Fungicidal pyrazoles

ABSTRACT

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, N-oxides, and salts thereof, 
     
       
         
         
             
             
         
       
     
     wherein
         Q 1 , Q 2 , X, R 1 , R 1a  and R 2  are as defined in the disclosure.
 
Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling plant disease caused by a fungal pathogen comprising applying an effective amount of a compound or a composition of the invention.

FIELD OF THE INVENTION

This invention relates to certain pyrazoles, their N-oxides, salts andcompositions, and methods of their use as fungicides.

BACKGROUND OF THE INVENTION

The control of plant diseases caused by fungal plant pathogens isextremely important in achieving high crop efficiency. Plant diseasedamage to ornamental, vegetable, field, cereal, and fruit crops cancause significant reduction in productivity and thereby result inincreased costs to the consumer. Many products are commerciallyavailable for these purposes, but the need continues for new compoundswhich are more effective, less costly, less toxic, environmentally saferor have different sites of action.

PCT Patent Publications WO 2009/137538, WO 2009/137651, WO 2010/101973,WO 2012/023143, WO 2012/030922 and WO 2012/031061 disclose pyrazolederivatives and their use as fungicides.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including allstereoisomers), N-oxides, and salts thereof, agricultural compositionscontaining them and their use as fungicides:

wherein

-   -   Q¹ is a phenyl ring or a naphthalenyl ring system, each ring or        ring system optionally substituted with up to 5 substituents        independently selected from R^(3a) and R^(3b); or a 5- to        6-membered fully unsaturated heterocyclic ring or an 8- to        10-membered heteroaromatic bicyclic ring system, each ring or        ring system containing ring members selected from carbon atoms        and 1 to 4 heteroatoms independently selected from up to 2 O, up        to 2 S and up to 4 N atoms, wherein up to 3 carbon ring members        are independently selected from C(═O) and C(═S), and the sulfur        atom ring members are independently selected from        S(═O)_(u)(═NR²⁷)_(v), each ring or ring system optionally        substituted with up to 5 substituents independently selected        from R^(3a) and R^(3b) on carbon atom ring members and selected        from cyano, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆        cycloalkyl, C₂-C₄ alkoxyalkyl, C₁-C₄ alkoxy, C₂-C₄        alkylcarbonyl, C₂-C₄ alkoxycarbonyl, C₂-C₄ alkylaminoalkyl and        C₃-C₄ dialkylaminoalkyl on nitrogen atom ring members;    -   Q² is a phenyl ring or a naphthalenyl ring system, each ring or        ring system optionally substituted with up to 5 substituents        independently selected from R^(3a) and R^(3b); or a 5- to        6-membered fully unsaturated heterocyclic ring or an 8- to        10-membered heteroaromatic bicyclic ring system, each ring or        ring system containing ring members selected from carbon atoms        and 1 to 4 heteroatoms independently selected from up to 2 O, up        to 2 S and up to 4 N atoms, wherein up to 3 carbon ring members        are independently selected from C(═O) and C(═S), and the sulfur        atom ring members are independently selected from        S(═O)_(u)(═NR²⁷)_(v), each ring or ring system optionally        substituted with up to 5 substituents independently selected        from R^(3a) and R^(3b) on carbon atom ring members and selected        from cyano, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆        cycloalkyl, C₂-C₄ alkoxyalkyl, C₁-C₄ alkoxy, C₂-C₄        alkylcarbonyl, C₂-C₄ alkoxycarbonyl, C₂-C₄ alkylaminoalkyl and        C₃-C₄ dialkylaminoalkyl on nitrogen atom ring members;    -   X is O, S(═O)_(m), NR⁴ or CR^(5a)OR^(5b);    -   R¹ is H, cyano, halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆        alkenyl, C₂-C₆ alkynyl, C₃-C₆ cycloalkyl, C₂-C₆ alkoxyalkyl,        C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, —C(═O)OR⁶ or —C(═O)NR⁷R⁸;    -   R^(1a) is H; or    -   R^(1a) and R¹ are taken together with the carbon atom to which        they are attached to form a cyclopropyl ring optionally        substituted with up to 2 substituents independently selected        from halogen and methyl;    -   R² is H, cyano, halogen, C₁-C₃ alkyl, C₂-C₃ alkenyl, C₂-C₃        alkynyl, C₁-C₃ haloalkyl, C₂-C₃ haloalkenyl, C₂-C₃ cyanoalkyl,        C₁-C₃ hydroxyalkyl, C₁-C₃ alkoxy or C₁-C₃ alkylthio; or        cyclopropyl optionally substituted with up to 2 substituents        independently selected from halogen and methyl;    -   each R^(3a) is independently amino, cyano, halogen, hydroxy,        nitro, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₄ alkenyl, C₂-C₄        alkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₄-C₆        cycloalkylalkyl, C₄-C₆ alkylcycloalkyl, C₁-C₃ alkylthio, C₁-C₃        haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃ haloalkylsulfinyl,        C₁-C₃ alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₁-C₃ alkoxy,        C₁-C₃ haloalkoxy, C₃-C₆ cycloalkoxy, C₁-C₃ alkylsulfonyloxy,        C₁-C₃ haloalkylsulfonyloxy, C₂-C₄ alkylcarbonyloxy, C₂-C₄        alkylcarbonyl, C₁-C₃ alkylamino, C₂-C₄ dialkylamino, C₂-C₄        alkylcarbonylamino, —CH(═O), —NHCH(═O), —SF₅, —SC≡N or —U—V-T;    -   each R^(3b) is independently C₄-C₈ alkyl, C₄-C₈ haloalkyl, C₅-C₈        alkenyl, C₂-C₈ haloalkenyl, C₅-C₈ alkynyl, C₂-C₈ haloalkynyl,        C₁-C₈ nitroalkyl, C₂-C₈ nitroalkenyl, C₇-C₈ cycloalkyl, C₇-C₈        halocycloalkyl, C₇-C₈ cycloalkylalkyl, C₇-C₈ alkylcycloalkyl,        C₅-C₁₂ cycloalkylalkenyl, C₅-C₁₂ cycloalkylalkynyl, C₆-C₁₂        cycloalkylcycloalkyl, C₄-C₈ alkylthio, C₄-C₈ haloalkythio, C₄-C₈        alkylsulfinyl, C₄-C₈ haloalkylsulfinyl, C₄-C₈ alkylsulfonyl,        C₄-C₈ haloalkylsulfonyl, C₄-C₈ alkoxy, C₄-C₈ haloalkoxy, C₂-C₈        alkenyloxy, C₂-C₈ haloalkenyloxy, C₃-C₈ alkynyloxy, C₃-C₈        haloalkynyloxy, C₇-C₁₂ cycloalkoxy, C₃-C₁₂ halocycloalkoxy,        C₄-C₁₂ cycloalkylalkoxy, C₅-C₁₂ cycloalkylalkenyloxy, C₅-C₁₂        cycloalkylalkynyloxy, C₄-C₈ alkylsulfonyloxy, C₄-C₈        haloalkylsulfonyloxy, C₅-C₈ alkylcarbonyloxy, C₅-C₈        alkylcarbonyl, C₄-C₈ alkylamino, C₅-C₈ alkylcarbonylamino,        C₃-C₁₂ trialkylsilyl, C₄-C₁₂ trialkylsilylalkyl, C₄-C₁₂        trialkylsilylalkoxy, —C(═S)NR^(9a)R^(9b), —CR^(10a)═NOR^(10b),        —CR^(10c)═NNR^(9a)R^(9b), —NR^(9a)N═CR^(11a)R^(11b),        —ON═CR^(11a)R^(11b) or -A(CR^(12a)R^(12b))_(n)W;    -   each A is independently O or a direct bond;    -   each W is independently a 3- to 7-membered heterocyclic ring        containing ring members selected from carbon atoms and 1 to 4        heteroatoms independently selected from up to 2 O, up to 2 S and        up to 4 N atoms, wherein up to 3 carbon atom ring members are        independently selected from C(═O) and C(═S), the ring optionally        substituted with up to 3 substituents independently selected        from R¹³ on carbon atom ring members and R¹⁴ on nitrogen atom        ring members;

R⁴ is H, amino, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, —CH(═O),—S(═O)₂OM, —S(═O)_(m)R¹⁵, —(C═Z)R¹⁶ or OR¹⁷; or C₁-C₆ alkyl or C₁-C₆haloalkyl, each optionally substituted with up to 2 substituentsindependently selected from R¹⁸;

-   -   R^(5a) is H or C₁-C₆ alkyl;    -   R^(5b) is H, —CH(═O), C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆        alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl,        C₂-C₆ cyanoalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆        alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₄-C₈        cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈        (cycloalkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl) or C₄-C₈        cycloalkoxy(thiocarbonyl);    -   R⁶ is H, C₁-C₆ alkyl or C₁-C₆ haloalkyl;    -   R⁷ and R⁸ are each independently H, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₃-C₆ cycloalkyl, C₄-C₈ cycloalkylalkyl or C₄-C₈        alkylcycloalkyl; or    -   R⁷ and R⁸ are taken together with the nitrogen atom to which        they are attached to form a 4- to 7-membered nonaromatic        heterocyclic ring containing ring members, in addition to the        connecting nitrogen atom, selected from carbon atoms and up to 1        ring member selected from O, S(═O)_(m) and NR¹⁹;    -   each R^(9a) and R^(9b) is independently H, C₁-C₄ alkyl or C₁-C₄        haloalkyl;    -   each R^(10a) is independently H, C₁-C₃ alkyl or C₁-C₃ haloalkyl;    -   each R^(10b) and R^(10c) is independently H, C₁-C₃ alkyl, C₁-C₃        haloalkyl, C₂-C₄ alkenyl, C₂-C₄ haloalkenyl, C₂-C₄ alkynyl,        C₃-C₄ cycloalkyl, C₃-C₄ halocycloalkyl or C₄-C₈ cycloalkylalkyl;    -   each R^(11a) and R^(11b) is independently H, C₁-C₃ alkyl or        C₁-C₃ haloalkyl;    -   each R^(12a) is independently H, cyano, halogen or C₁-C₄ alkyl;    -   each R^(12b) is independently H or C₁-C₄ alkyl;    -   each R¹³ is independently cyano, halogen, C₁-C₂ alkyl, C₁-C₂        haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy or C₂-C₄ alkoxyalkyl;    -   each R¹⁴ is independently cyano, C₁-C₂ alkyl or C₁-C₂ alkoxy;    -   R¹⁵ is C₁-C₆ alkyl or C₁-C₆ haloalkyl;    -   R¹⁶ is C₁-C₆ alkyl, C₂-C₆ alkylthioalkyl, C₂-C₆ alkoxyalkyl,        C₂-C₆ alkylaminoalkyl, C₃-C₆ dialkylaminoalkyl, C₁-C₆ alkoxy or        C₁-C₆ alkylthio;    -   R¹⁷ is H, —CH(═O), C₃-C₆ cycloalkyl, —S(═O)₂OM or —(C═Z)R²⁰; or        C₁-C₆ alkyl or C₁-C₆ haloalkyl, each optionally substituted with        up to 2 substituents independently selected from R²¹;    -   each R¹⁸ and R²¹ is independently cyano, C₃-C₆ cycloalkyl, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy, C₁-C₆ alkylthio, C₁-C₆ alkylsulfinyl        or C₁-C₆ alkylsulfonyl;    -   R¹⁹ is H, C₁-C₃ alkyl or C₂-C₃ haloalkyl;    -   R²⁰ is C₁-C₆ alkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylthioalkyl,        C₂-C₆ alkylaminoalkyl, C₃-C₆ dialkylaminoalkyl, C₁-C₆ alkoxy or        C₁-C₆ alkylthio;    -   each U is independently O, S(═O)_(m), NR²² or a direct bond;    -   each V is independently C₁-C₆ alkylene, C₂-C₆ alkenylene, C₃-C₆        alkynylene, C₃-C₆ cycloalkylene or C₃-C₆ cycloalkenylene,        wherein up to 3 carbon atoms are C(═O), each optionally        substituted with up to 5 substituents independently selected        from halogen, cyano, nitro, hydroxy, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₁-C₆ alkoxy and C₁-C₆ haloalkoxy;    -   each T is independently cyano, NR^(23a)R^(23b), OR²⁴ or        S(═O)_(m)R²⁵;    -   each R²² is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆        alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl,        C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈ cycloalkylcarbonyl, C₄-C₈        cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl or C₄-C₈        cycloalkoxy(thiocarbonyl);    -   each R^(23a) and R^(23b) is independently H, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆        (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl), C₄-C₈        cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈        (cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); or        a pair of R^(23a) and R^(23b) attached to the same nitrogen atom        are taken together with the nitrogen atom to form a 3- to        6-membered heterocyclic ring, the ring optionally substituted        with up to 5 substituents independently selected from R²⁶;    -   each R²⁴ and R²⁵ is independently H, C₁-C₆ alkyl, C₁-C₆        haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆        (alkylthio)carbonyl, C₄-C₈ cycloalkylcarbonyl, C₄-C₈        cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl, C₂-C₆        alkoxy(thiocarbonyl) or C₄-C₈ cycloalkoxy(thiocarbonyl);    -   each R²⁶ is independently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl        or C₁-C₆ alkoxy;    -   each R²⁷ is independently H, cyano, C₁-C₃ alkyl or C₁-C₃        haloalkyl;    -   Z is O or S;    -   M is K, Na or Li;    -   each m is independently 0, 1 or 2;    -   each n is independently 0, 1, 2 or 3; and    -   each u and v are independently 0, 1 or 2 in each instance of        S(═O)_(u)(═NR²⁷)_(v); provided that:    -   (a) the sum of u and v is 0, 1 or 2;    -   (b) when Q¹ and Q² are each an optionally substituted phenyl        ring, an optionally substituted naphthalenyl ring system, an        optionally substituted 5- to 6-membered fully unsaturated        heterocyclic ring or an optionally substituted 8- to 10-membered        heteroaromatic bicyclic ring system, then at least one of Q¹ or        Q² is substituted with at least one R^(3b); and    -   (c) when n is 1, 2, or 3, then W is linked through a carbon atom        to the remainder of Formula 1.

More particularly, this invention pertains to a compound selected fromcompounds of Formula 1 (including all stereoisomers) and N-oxides andsalts thereof.

This invention also relates to a fungicidal composition comprising (a) acompound of the invention (i.e. in a fungicidally effective amount); and(b) at least one additional component selected from the group consistingof surfactants, solid diluents and liquid diluents.

This invention also relates to a fungicidal composition comprising (a) acompound of the invention; and (b) at least one other fungicide (e.g.,at least one other fungicide having a different site of action).

This invention further relates to a method for controlling plantdiseases caused by fungal plant pathogens comprising applying to theplant or portion thereof, or to the plant seed, a fungicidally effectiveamount of a compound of the invention (e.g., as a composition describedherein).

This invention also relates to a composition comprising a compound ofFormula 1, an N-oxide, or a salt thereof, and at least one invertebratepest control compound or agent.

DETAILS OF THE INVENTION

As used herein, the terms “comprises”, “comprising”, “includes”,“including”, “has”, “having”, “contains”, “containing”, “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process, method, article, orapparatus that comprises a list of elements is not necessarily limitedto only those elements but may include other elements not expresslylisted or inherent to such composition, mixture, process, method,article, or apparatus.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition, method or apparatus that includes materials, steps,features, components, or elements, in addition to those literallydisclosed, provided that these additional materials, steps, features,components, or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in the present disclosure and claims, “plant” includesmembers of Kingdom Plantae, particularly seed plants (Spermatopsida), atall life stages, including young plants (e.g., germinating seedsdeveloping into seedlings) and mature, reproductive stages (e.g., plantsproducing flowers and seeds). Portions of plants include geotropicmembers typically growing beneath the surface of the growing medium(e.g., soil), such as roots, tubers, bulbs and corms, and also membersgrowing above the growing medium, such as foliage (including stems andleaves), flowers, fruits and seeds.

As referred to herein, the term “seedling”, used either alone or in acombination of words means a young plant developing from the embryo of aseed.

As referred to herein, the term “broadleaf” used either alone or inwords such as “broadleaf crop” means dicot or dicotyledon, a term usedto describe a group of angiosperms characterized by embryos having twocotyledons.

As used herein, the term “alkylating agent” refers to a chemicalcompound in which a carbon-containing radical is bound through a carbonatom to a leaving group such as halide or sulfonate, which isdisplaceable by bonding of a nucleophile to said carbon atom. Unlessotherwise indicated, the term “alkylating agent” or “alkylating reagent”does not limit the carbon-containing radical to alkyl; thecarbon-containing radicals in alkylating agents include the variety ofcarbon-bound substituent radicals specified, for example, for R¹ and R².

Generally when a molecular fragment (i.e. radical) is denoted by aseries of atom symbols (e.g., C, H, N, O and S) the implicit point orpoints of attachment will be easily recognized by those skilled in theart. In some instances herein, particularly when alternative points ofattachment are possible, the point or points of attachment may beexplicitly indicated by a hyphen (“-”). For example, “—SCN” indicatesthat the point of attachment is the sulfur atom (i.e. thiocyanato, notisothiocyanato).

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl such as methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl”includes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.“Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” also includes moieties comprisedof multiple triple bonds such as 2,5-hexadiynyl. “Alkylene” denotes astraight-chain or branched alkanediyl. Examples of “alkylene” includeCH₂, CH₂CH₂, CH(CH₃), CH₂CH₂CH₂, CH₂CH(CH₃), and the different butylene,pentylene or hexylene isomers. “Alkenylene” denotes a straight-chain orbranched alkenediyl containing one olefinic bond. Examples of“alkenylene” include CH═CH, CH₂CH═CH and CH═C(CH₃). “Alkynylene” denotesa straight-chain or branched alkynediyl containing one triple bond.Examples of “alkynylene” include CH₂C≡C, C≡CCH₂, and the differentbutynylene, pentynylene or hexynylene isomers.

“Alkylamino” includes an NH radical substituted with straight-chain orbranched alkyl. Examples of “alkylamino” include CH₃CH₂NH, CH₃CH₂CH₂NHand (CH₃)₂CHNH. Examples of “dialkylamino” include (CH₃)₂N, (CH₃CH₂)₂Nand CH₃CH₂(CH₃)N. “Alkylaminoalkyl” denotes alkylamino substitution onalkyl. Examples of “alkylaminoalkyl” include CH₃NHCH₂, CH₃NHCH₂CH₂ andCH₃CH₂NHCH₂. Examples of “dialkylaminoalkyl” include (CH₃)₂NCH₂,CH₃CH₂(CH₃)NCH₂ and (CH₃)₂NCH₂CH₂.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy,i-propyloxy and the different butoxy, pentoxy and hexyloxy isomers.“Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of“alkoxyalkyl” include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂and CH₃CH₂OCH₂CH₂. “Alkenyloxy” includes straight-chain or branchedalkenyl attached to and linked through an oxygen atom. Examples of“alkenyloxy” include H₂C═CHCH₂O, (CH₃)₂C═CHCH₂O, CH₃CH═CHCH₂O,CH₃CH═C(CH₃)CH₂O and H₂C═CHCH₂CH₂O. “Alkynyloxy” includes straight-chainor branched alkynyl attached to and linked through an oxygen atom.Examples of “alkynyloxy” include HC≡CCH₂O, CH₃C≡CCH₂O and CH₃C≡CCH₂CH₂O.The term “alkylsulfonyloxy” denotes alkylsulfonyl attached to and linkedthrough an oxygen atom. Examples of “alkylsulfonyloxy” includeCH₃S(═O)₂O, CH₃CH₂S(═O)₂O, CH₃CH₂CH₂S(═O)₂O and (CH₃)₂CHS(═O)₂O.

“Alkylthio” includes branched or straight-chain alkylthio moieties suchas methylthio, ethylthio, and the different propylthio isomers.“Alkylthioalkyl” denotes alkylthio substitution on alkyl. Examples of“alkylthioalkyl” include CH₃SCH₂, CH₃SCH₂CH₂, CH₃CH₂SCH₂,CH₃CH₂CH₂CH₂SCH₂ and CH₃CH₂SCH₂CH₂. “Alkylsulfinyl” includes bothenantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl”include CH₃S(═O), CH₃CH₂S(═O), CH₃CH₂CH₂S(═O) and (CH₃)₂CHS(═O).Examples of “alkylsulfonyl” include CH₃S(═O)₂, CH₃CH₂S(═O)₂,CH₃CH₂CH₂S(═O)₂ and (CH₃)₂CHS(═O)₂.

The term “cycloalkyl” denotes a saturated carbocyclic ring consisting ofbetween 3 to 8 carbon atoms linked to one another by single bonds.Examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyland cyclohexyl. The term “cycloalkylalkyl” denotes cycloalkylsubstitution on an alkyl group. Examples of “cycloalkylalkyl” includecyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moietiesbonded to straight-chain or branched alkyl groups. “Alkylcycloalkyl”denotes alkyl substitution on a cycloalkyl moiety. Examples include4-methylcyclohexyl and 3-ethylcyclopentyl. The term“cycloalkylcycloalkyl” denotes cycloalkyl substitution on anothercycloalkyl ring, wherein each cycloalkyl ring independently has from 3to 6 carbon atom ring members. Examples of “cycloalkylcycloalkyl”include cyclopropylcyclopropyl (such as 1,1′-bicyclopropyl-1-yl,1,1′-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as1,1′-bicyclohexyl-1-yl), and the different cis- andtrans-cycloalkylcycloalkyl isomers, (such as(1R,2S)-1,1′-bicyclopropyl-2-yl and (1R,2R)-1,1′-bicyclopropyl-2-yl).The term “cycloalkoxy” denotes cycloalkyl attached to and linked throughan oxygen atom such as cyclopentyloxy and cyclohexyloxy.“Cycloalkylalkoxy” denotes cycloalkyl substitution on an alkoxy group.Examples of “cycloalkylalkoxy” include cyclopropylmethoxy,cyclopentylethoxy, and other cycloalkyl moieties bonded tostraight-chain or branched alkoxy groups. “Cycloalkylcarbonyl” denotescycloalkyl bonded to a C(═O) group including, for example,cyclopropylcarbonyl and cyclopentylcarbonyl. The term“cycloalkoxycarbonyl” means cycloalkoxy bonded to a C(═O) group, forexample, cyclopropyloxycarbonyl and cyclopentyloxycarbonyl. The term“cycloalkylene” denotes a cycloalkanediyl ring. Examples of“cycloalkylene” include cyclopropylene, cyclobutylene, cyclopentyleneand cyclohexylene. The term “cycloalkenylene” denotes a cycloalkenediylring containing one olefinic bond. Examples of“cycloalkenylene” includecyclopropenylene and cyclopentenylene.

“Cyanoalkyl” denotes an alkyl group substituted with one cyano group.Examples of “cyanoalkyl” include NCCH₂, NCCH₂CH₂ and CH₃CH(CN)CH₂.“Hydroxyalkyl” denotes an alkyl group substituted with one hydroxygroup. Examples of “hydroxyalkyl” include HOCH₂, HOCH₂CH₂ andCH₃CH₂(OH)CH. “Nitroalkyl” denotes an alkyl group substituted with onenitro group. Examples of “nitroalkyl” include NO₂CH₂ and NO₂CH₂CH₂.

“Alkylcarbonyl” denotes a straight-chain or branched alkyl group bondedto a C(═O) moiety. Examples of “alkylcarbonyl” include CH₃C(═O),CH₃CH₂CH₂C(═O) and (CH₃)₂CHC(═O). Examples of “alkoxycarbonyl” includeCH₃OC(═O), CH₃CH₂OC(═O), CH₃CH₂CH₂OC(═O), (CH₃)₂CHOC(═O) and thedifferent pentoxy- or hexoxycarbonyl isomers. The term“alkylcarbonyloxy” denotes a straight-chain or branched alkyl bonded toa C(═O)O moiety. Examples of “alkylcarbonyloxy” include CH₃CH₂C(═O)O and(CH₃)₂CHC(═O)O. “(Alkylthio)carbonyl” denotes a straight-chain orbranched alkylthio group bonded to a C(═O) moiety. Examples of“(alkylthio)carbonyl” include CH₃SC(═O), CH₃CH₂CH₂SC(═O) and(CH₃)₂CHSC(═O). “Alkoxy(thiocarbonyl)” denotes a straight-chain orbranched alkoxy group bonded to a C(═S) moiety. Examples of“alkoxy(thiocarbonyl)” include CH₃OC(═S), CH₃CH₂CH₂OC(═S) and(CH₃)₂CHOC(═S). The term “alkylcarbonylamino” denotes alkyl bonded to aC(═O)NH moiety. Examples of “alkylcarbonylamino” include CH₃C(═O)NH andCH₃CH₂C(═O)NH.

“Trialkylsilyl” includes 3 branched and/or straight-chain alkyl radicalsattached to and linked through a silicon atom, such as trimethylsilyl,triethylsilyl and tert-butyldimethylsilyl.

The term “halogen”, either alone or in compound words such as“halomethyl”, “haloalkyl”, includes fluorine, chlorine, bromine oriodine. Further, when used in compound words such as “haloalkyl”, saidalkyl may be partially or fully substituted with halogen atoms which maybe the same or different. Examples of “haloalkyl” include F₃C, ClCH₂,CF₃CH₂ and CF₃CCl₂. The terms “haloalkenyl”, “haloalkoxy”,“haloalkylthio”, “haloalkylsulfinyl” “haloalkylsulfonyl” and“halocycloalkyl” are defined analogously to the term “haloalkyl”.Examples of “haloalkenyl” include Cl₂C═CHCH₂ and CF₃CH₂═CH. Examples of“haloalkoxy” include CF₃O, CCl₃CH₂O, F₂CHCH₂CH₂O and CF₃CH₂O. Examplesof “haloalkylthio” include CCl₃S, CF₃S, CCl₃CH₂S and ClCH₂CH₂CH₂S.Examples of “haloalkylsulfinyl” include CF₃S(═O), CCl₃S(═O), CF₃CH₂S(═O)and CF₃CF₂S(═O). Examples of “haloalkylsulfonyl” include CF₃S(═O)₂,CCl₃S(═O)₂, CF₃CH₂S(═O)₂ and CF₃CF₂S(═O)₂. Examples of “halocycloalkyl”include chlorocyclopropyl, fluorocyclobutyl and chlorocyclohexyl.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 12. Forexample, C₁-C₃ alkylsulfonyl designates methylsulfonyl throughpropylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂; C₃ alkoxyalkyldesignates, for example, CH₃OCH₂CH₂ or CH₃CH₂OCH₂; and C₄ alkoxyalkyldesignates the various isomers of an alkyl group substituted with analkoxy group containing a total of four carbon atoms, examples includingCH₃CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.

The term “unsubstituted” in connection with a group such as a ring meansthe group does not have any substituents other than its one or moreattachments to the remainder of Formula 1. The term “optionallysubstituted” means that the number of substituents can be zero. Unlessotherwise indicated, optionally substituted groups may be substitutedwith as many optional substituents as can be accommodated by replacing ahydrogen atom with a non-hydrogen substituent on any available carbon ornitrogen atom. Commonly, the number of optional substituents (whenpresent) range from 1 to 3. As used herein, the term “optionallysubstituted” is used interchangeably with the phrase “substituted orunsubstituted” or with the term “(un)substituted.”

The number of optional substituents may be restricted by an expressedlimitation. For example, the phrase “optionally substituted with up to 3substituents independently selected from R^(3a) on carbon atom ringmembers” means that 0, 1, 2 or 3 substituents can be present (if thenumber of potential connection points allows). Similarly, the phrase“optionally substituted with up to 5 substituents independently selectedfrom R^(3a)” means that 0, 1, 2, 3, 4 or 5 substituents can be presentif the number of available connection points allows.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can vary (e.g.,(R^(3a))_(p) in Table 1 wherein p is 0 to 5), then said substituents areindependently selected from the group of defined substituents, unlessotherwise indicated. When a variable group is shown to be optionallyattached to a position, for example (R^(3a))_(p) in Table 1 wherein pmay be 0, then hydrogen may be at the position even if not recited inthe definition of the variable group.

Unless otherwise indicated, a “ring” or “ring system” as a component ofFormula 1 (e.g., Q¹ or Q²) is carbocyclic (e.g., phenyl or naphthalenyl)or heterocyclic (e.g., pyridinyl). The term “ring member” refers to anatom (e.g., C, O, N or S) forming the backbone of a ring. The term “ringsystem” denotes two or more fused rings (e.g., quinazolinyl).

The term “nonaromatic” includes rings that are fully saturated as wellas partially or fully unsaturated, provided that none of the rings arearomatic. The term “aromatic” indicates that each of the ring atoms of afully unsaturated ring are essentially in the same plane and have ap-orbital perpendicular to the ring plane, and that (4n+2) π electrons,where n is a positive integer, are associated with the ring to complywith Hickel's rule.

The terms “carbocyclic ring” or “carbocycle” denote a ring wherein theatoms forming the ring backbone are selected only from carbon. When afully unsaturated carbocyclic ring satisfies Hickel's rule, then saidring is also called an “aromatic carbocyclic ring”. The term “saturatedcarbocyclic ring” refers to a ring having a backbone consisting ofcarbon atoms linked to one another by single bonds; unless otherwisespecified, the remaining carbon valences are occupied by hydrogen atoms.

The terms “heterocyclic ring”, “heterocycle” or “heteroaromatic ringsystem” denote a ring or ring system in which at least one atom formingthe ring backbone is not carbon (e.g., N, O or S). Typically aheterocyclic ring contains no more than 3 N atoms, no more than 2 Oatoms and no more than 2 S atoms. Unless otherwise indicated, aheterocyclic ring can be a saturated, partially unsaturated or fullyunsaturated ring. When a fully unsaturated heterocyclic ring satisfiesHickel's rule, then said ring is also called a “heteroaromatic ring” or“aromatic heterocyclic ring”. Unless otherwise indicated, heterocyclicrings can be attached through any available carbon or nitrogen byreplacement of a hydrogen on said carbon or nitrogen.

In the context of the present invention when an instance of Q¹ and Q²comprises a phenyl or 6-membered heterocyclic ring (e.g., pyridinyl),the ortho, meta and para positions of each ring are relative to theconnection of the ring to the remainder of Formula 1.

Compounds of this invention can exist as one or more stereoisomers. Thevarious stereoisomers include enantiomers, diastereomers, atropisomersand geometric isomers. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. The compounds of the invention may be present as amixture of stereoisomers, individual stereoisomers or as an opticallyactive form.

One skilled in the art recognizes that some of the compounds disclosedherein can exist in equilibrium with one or more of their respectivetautomeric counterparts. Unless otherwise indicated, reference to acompound by one tautomer description is to be considered to include alltautomers.

One skilled in the art recognizes that because in the environment andunder physiological conditions salts of chemical compounds are inequilibrium with their corresponding nonsalt forms, salts share thebiological utility of the nonsalt forms. Thus a wide variety of salts ofthe compounds of Formula 1 are useful for control of plant diseasescaused by fungal plant pathogens (i.e. are agriculturally suitable). Thesalts of the compounds of Formula 1 include acid-addition salts withinorganic or organic acids such as hydrobromic, hydrochloric, nitric,phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic,oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valericacids.

Compounds selected from Formula 1, stereoisomers, N-oxides, and saltsthereof, typically exist in more than one form, therefore Formula 1includes all crystalline and non-crystalline forms of the compounds thatFormula 1 represents. Non-crystalline forms include embodiments whichare solids such as waxes and gums as well as embodiments which areliquids such as solutions and melts. Crystalline forms includeembodiments which represent essentially a single crystal type andembodiments which represent a mixture of polymorphs (i.e. differentcrystalline types). The term “polymorph” refers to a particularcrystalline form of a chemical compound that can crystallize indifferent crystalline forms, these forms having different arrangementsand/or conformations of the molecules in the crystal lattice. Althoughpolymorphs can have the same chemical composition, they can also differin composition due to the presence or absence of co-crystallized wateror other molecules, which can be weakly or strongly bound in thelattice. Polymorphs can differ in such chemical, physical and biologicalproperties as crystal shape, density, hardness, color, chemicalstability, melting point, hygroscopicity, suspensibility, dissolutionrate and biological availability. One skilled in the art will appreciatethat a polymorph of a compound represented by Formula 1 can exhibitbeneficial effects (e.g., suitability for preparation of usefulformulations, improved biological performance) relative to anotherpolymorph or a mixture of polymorphs of the same compound represented byFormula 1. Preparation and isolation of a particular polymorph of acompound represented by Formula 1 can be achieved by methods known tothose skilled in the art including, for example, crystallization usingselected solvents and temperatures.

Embodiments of the present invention as described in the Summary of theInvention include those described below. In the following Embodiments,Formula 1 includes stereoisomers, N-oxides and salts thereof, andreference to “a compound of Formula 1” includes the definitions ofsubstituents specified in the Summary of the Invention unless furtherdefined in the Embodiments.

Embodiment 1

A compound of Formula 1 wherein Q¹ is a phenyl, pyridinyl, pyrimidinyl,pyrazinyl or pyridazinyl ring, each ring optionally substituted with upto 3 substituents independently selected from R^(3a) and R^(3b).

Embodiment 2

A compound of Embodiment 1 wherein Q¹ is a phenyl ring optionallysubstituted with up to 3 substituents independently selected from R^(3a)and R^(3b).

Embodiment 3

A compound of Formula 1 wherein Q¹ is a phenyl ring optionallysubstituted with up to 2 substituents independently selected from R^(3a)and substituted with 1 to 2 substituents independently selected fromR^(3b).

Embodiment 4

A compound of Embodiment 3 wherein Q¹ is a phenyl ring optionallysubstituted with up to 2 substituents independently selected from R^(3a)and substituted with 1 substituent selected from R^(3b).

Embodiment 5

A compound of Embodiment 4 wherein Q¹ is a phenyl ring optionallysubstituted with up to 1 substituent selected from R^(3a) andsubstituted with 1 substituent selected from R^(3b).

Embodiment 6

A compound of Formula 1 or any one of Embodiments 1 through 5 wherein Q¹is a phenyl ring substituted with 1 to 3 substituents independentlyselected from R^(3a) and R^(3b).

Embodiment 7

A compound of Embodiment 6 wherein Q¹ is a phenyl ring substituted with2 substituents independently selected from R^(3a) and 1 substituentselected from R^(3b).

Embodiment 8

A compound of Embodiment 7 wherein Q¹ is a phenyl ring substituted with1 substituent selected from R^(3a) and 1 substituent selected fromR^(3b).

Embodiment 9

A compound of Formula 1 or any one of Embodiments 1 through 8 wherein Q¹is a phenyl ring substituted with at least 1 substituent selected fromR^(3a) which is attached at an ortho position (relative to theconnection of the Q¹ ring to the remainder of Formula 1).

Embodiment 10

A compound of Formula 1 or any one of Embodiments 1 through 9 wherein Q¹is a phenyl ring substituted with at least 1 substituent selected fromR^(3b) which is attached at the para position (relative to theconnection of the Q¹ ring to the remainder of Formula 1).

Embodiment 11

A compound of Formula 1 or any one of Embodiments 1 through 10 whereinQ¹ is a phenyl ring substituted with 2 substituents independentlyselected from R^(3a) which are attached at the 2- and 6-positions and 1substituent selected from R^(3b) which is attached at the 4-position(relative to the connection of the Q¹ ring to the remainder of Formula1).

Embodiment 12

A compound of Formula 1 or any one of Embodiments 1 through 11 whereinQ¹ is a phenyl ring substituted at the 2-, 4- and 6-positions withsubstituents independently selected from R^(3a) and R^(3b); or a phenylring substituted at the 2- and 4-positions with substituentsindependently selected from R^(3a) and R^(3b); or a phenyl ringsubstituted at the 2- and 6-positions with substituents independentlyselected from R^(3a) and R^(3b) (relative to the connection of the Q¹ring to the remainder of Formula 1).

Embodiment 13

A compound of Formula 1 or any one of Embodiments 1 through 12 whereinQ² is a phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl ring,each ring optionally substituted with up to 3 substituents independentlyselected from R^(3a) and R^(3b).

Embodiment 14

A compound of Embodiment 13 wherein Q² is a phenyl ring optionallysubstituted with up to 3 substituents independently selected from R^(3a)and R^(3b).

Embodiment 15

A compound of Embodiment 14 wherein Q² is a phenyl ring optionallysubstituted with up to 2 substituents independently selected from R^(3a)and R^(3b).

Embodiment 16

A compound of Embodiment 14 wherein Q² is a phenyl ring substituted with1 to 3 substituents independently selected from R^(3a).

Embodiment 17

A compound of Embodiment 16 wherein Q² is a phenyl ring substituted with3 substituents independently selected from R^(3a).

Embodiment 18

A compound of Embodiment 17 wherein Q² is a phenyl ring substituted with2 substituents independently selected from R^(3a).

Embodiment 19

A compound of Formula 1 or any one of Embodiments 1 through 18 whereinQ² is a phenyl ring substituted with 1 to 3 substituents independentlyselected from R^(3a) and R^(3b).

Embodiment 20

A compound of Embodiment 19 wherein Q² is a phenyl ring substituted with2 substituents independently selected from R^(3a) and 1 substituentselected from R^(3b).

Embodiment 21

A compound of Embodiment 20 wherein Q² is a phenyl ring substituted with1 substituent selected from R^(3a) and 1 substituent selected fromR^(3b).

Embodiment 22

A compound of Formula 1 or any one of Embodiments 1 through 21 whereinQ² is a phenyl ring substituted with at least 1 substituent selectedfrom R^(3a) which is attached at an ortho position (relative to theconnection of the Q² ring to the remainder of Formula 1).

Embodiment 23

A compound of Formula 1 or any one of Embodiments 1 through 22 whereinQ² is a phenyl ring substituted with at least 1 substituent selectedfrom R^(3b) which is attached at the para position (relative to theconnection of the Q² ring to the remainder of Formula 1).

Embodiment 24

A compound of Formula 1 or any one of Embodiments 1 through 23 whereinQ² is a phenyl ring substituted with at least 2 substituentsindependently selected from R^(3a) which are attached at the 2- and6-positions (relative to the connection of the Q² ring to the remainderof Formula 1).

Embodiment 24a

A compound of Formula 1 or any one of Embodiments 1 through 24 whereinQ² is a phenyl ring substituted with at least 2 substituentsindependently selected from R^(3a) which are attached at the 2- and4-positions (relative to the connection of the Q² ring to the remainderof Formula 1).

Embodiment 25

A compound of Formula 1 or any one of Embodiments 1 through 24a whereinQ² is a phenyl ring substituted with 2 substituents independentlyselected from R^(3a) which are attached at the 2- and 6-positions; or aphenyl ring substituted with 2 substituents independently selected fromR^(3a) which are attached at the 2- and 4-positions (relative to theconnection of the Q² ring to the remainder of Formula 1).

Embodiment 26

A compound of Formula 1 or any one of Embodiments 1 through 25 whereinQ² is a phenyl ring substituted with 2 substituents independentlyselected from R^(3a) which are attached at the 2- and 4-positions(relative to the connection of the Q² ring to the remainder of Formula1).

Embodiment 27

A compound of Formula 1 or any one of Embodiments 1 through 26 whereinQ² is a phenyl ring substituted at the 2-, 4- and 6-positions withsubstituents independently selected from R^(3a) and R^(3b); or a phenylring substituted at the 2- and 4-positions with substituentsindependently selected from R^(3a) and R^(3b); or a phenyl ringsubstituted at the 2- and 6-positions with substituents independentlyselected from R^(3a) and R^(3b).

Embodiment 28

A compound of Formula 1 or any one of Embodiments 1 through 27 whereinwhen each Q¹ and Q² is a phenyl ring, then one of the Q¹ and Q² rings issubstituted with 2 or 3 substituents and the other of the Q¹ and Q²rings is substituted with 1 or 2 substituents.

Embodiment 29

A compound of Formula 1 or any one of Embodiments 1 through 28 whereinwhen each Q¹ and Q² is a phenyl ring, then Q¹ is substituted with 3substituents and Q² is substituted with 2 substituents.

Embodiment 30

A compound of Formula 1 or any one of Embodiments 1 through 29 wherein Xis O, S, NR⁴ or CR^(5a)OR^(5b).

Embodiment 31

A compound of Embodiment 30 wherein X is O, NR⁴ or CHOR^(5b).

Embodiment 32

A compound of Embodiment 31 wherein X is NR⁴ or CHOR^(5b).

Embodiment 33

A compound of Embodiment 32 wherein X is CHOR^(5b).

Embodiment 34

A compound of Embodiment 33 wherein X is CHOH.

Embodiment 35

A compound of Embodiment 32 wherein X is NR⁴.

Embodiment 36

A compound of Formula 1 or any one of Embodiments 1 through 35 whereinwhen R¹ is taken alone (i.e. not taken together with R^(1a)), then R¹ isH, cyano, halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₄ alkenyl, C₂-C₄alkynyl, cyclopropyl, C₂-C₄ alkoxyalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy,—C(═O)OR⁶ or —C(═O)NR⁷R⁸.

Embodiment 37

A compound of Embodiment 36 wherein R¹ is H, cyano, halogen, C₁-C₃alkyl, C₁-C₃ haloalkyl, C₂-C₄ alkoxyalkyl, C₁-C₃ alkoxy or C₁-C₃haloalkoxy.

Embodiment 38

A compound of Embodiment 37 wherein R¹ is H, cyano, halogen, C₁-C₃alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkoxy.

Embodiment 39

A compound of Embodiment 38 wherein R¹ is H, halogen or C₁-C₃ alkyl.

Embodiment 40

A compound of Embodiment 39 wherein R¹ is H or methyl.

Embodiment 41

A compound of Embodiment 40 wherein R¹ is H.

Embodiment 42

A compound of Formula 1 or any one of Embodiments 1 through 41 whereinR¹ is taken alone.

Embodiment 43

A compound of Formula 1 or any one of Embodiments 1 through 42 whereinR^(1a) is H.

Embodiment 44

A compound of Formula 1 or any one of Embodiments 1 through 43 whereinR^(1a) is taken alone.

Embodiment 45

A compound of Formula 1 or any one of Embodiments 1 through 44 whereinwhen R^(1a) and R¹ are taken together with the carbon atom to which theyare attached to form a ring, then said ring is cyclopropyl (i.e.unsubstituted).

Embodiment 46

A compound of Formula 1 or any one of Embodiments 1 through 45 whereinR^(1a) and R¹ are taken together.

Embodiment 47

A compound of Formula 1 or any one of Embodiments 1 through 46 whereinR² is cyano, halogen, C₁-C₂ alkyl, halomethyl, cyanomethyl,hydroxymethyl, methoxy or methylthio; or cyclopropyl optionallysubstituted with up to 2 substituents independently selected fromhalogen and methyl.

Embodiment 48

A compound of Embodiment 47 wherein R² is Br, Cl, I or C₁-C₂ alkyl.

Embodiment 49

A compound of Embodiment 48 wherein R² is Br, Cl or methyl.

Embodiment 50

A compound of Embodiment 49 wherein R² is methyl.

Embodiment 51

A compound of Formula 1 or any one of Embodiments 1 through 50 whereineach R^(3a) is independently amino, cyano, halogen, C₁-C₃ alkyl, C₁-C₃haloalkyl, C₂-C₄ alkenyl, C₃-C₄ cycloalkyl, C₄-C₆ cycloalkylalkyl, C₄-C₆alkylcycloalkyl, C₁-C₃ alkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy, C₃-C₆ cycloalkoxy, C₁-C₃alkylsulfonyloxy, C₂-C₄ alkylcarbonyloxy, C₂-C₄ alkylcarbonyl, C₁-C₃alkylamino, C₂-C₄ dialkylamino, C₂-C₄ alkylcarbonylamino, —CH(═O),—NHCH(═O), —SF₅, —SC≡N or —U—V-T.

Embodiment 52

A compound of Embodiment 51 wherein each R^(3a) is independently cyano,halogen, methyl, halomethyl, cyclopropyl, methylthio, methoxy,methylsulfonyloxy, methylcarbonyloxy, methylcarbonyl or —U—V-T.

Embodiment 53

A compound of Embodiment 52 wherein each R^(3a) is independently cyano,halogen, methyl, halomethyl or methoxy.

Embodiment 54

A compound of Embodiment 53 wherein each R^(3a) is independently cyano,halogen or methoxy.

Embodiment 55

A compound of Embodiment 54 wherein each R^(3a) is independently cyano,Br, Cl, F or methoxy.

Embodiment 56

A compound of Embodiment 55 wherein each R^(3a) is independently Br, Clor F.

Embodiment 57

A compound of Formula 1 or any one of Embodiments 1 through 56 whereineach R^(3b) is independently C₂-C₄ haloalkenyl, C₅-C₈ cycloalkylalkenyl,C₅-C₈ cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆ haloalkoxy, C₂-C₆alkenyloxy, C₂-C₆ haloalkenyloxy, C₃-C₆ alkynyloxy, C₃-C₆haloalkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₆ alkylsulfonyloxy, C₄-C₆haloalkylsulfonyloxy, C₃-C₉ trialkylsilyl, C₄-C₉ trialkylsilylalkyl,C₄-C₉ trialkylsilylalkoxy, —C(═S)NR^(9a)R^(9b), —CR^(10a)═NOR^(10b),—ON═CR^(11a)R^(11b) or -A(CR^(12a)R^(12b))_(n)W.

Embodiment 58

A compound of Embodiment 57 wherein each R^(3b) is independently C₅-C₈cycloalkylalkenyl, C₅-C₈ cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆haloalkoxy, C₂-C₆ alkenyloxy, C₂-C₆ haloalkenyloxy, C₃-C₆ alkynyloxy,C₃-C₆ haloalkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₆ alkylsulfonyloxy,C₄-C₆ haloalkylsulfonyloxy, C₄-C₉ trialkylsilylalkoxy,—C(═S)NR^(9a)R^(9b), —CR^(10a)═NOR^(10b), —ON═CR^(11a)R^(11b) or-A(CR^(12a)R^(12b))_(n)W.

Embodiment 59

A compound of Embodiment 58 wherein each R^(3b) is independently C₅-C₈cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆ haloalkoxy, C₂-C₆ alkenyloxy,C₂-C₆ haloalkenyloxy, C₃-C₆ alkynyloxy, C₃-C₆ haloalkynyloxy, C₄-C₈cycloalkylalkoxy, C₄-C₉ trialkylsilylalkoxy, —C(═S)NR^(9a)R^(9b),—CR^(10a)═NOR^(10b), —ON═CR^(11a)R^(11b) or -A(CR^(12a)R^(12b))_(n)W.

Embodiment 60

A compound of Embodiment 59 wherein each R^(3b) is independently C₅-C₈cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆ haloalkoxy, C₂-C₆ alkenyloxy,C₂-C₆ haloalkenyloxy, C₃-C₆ alkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₉trialkylsilylalkoxy, —C(═S)NR^(9a)R^(9b), —CR^(10a)═NOR^(10b),—ON═CR^(11a)R^(11b) or -A(CR^(12a)R^(12b))_(n)W.

Embodiment 61

A compound of Embodiment 60 wherein each R^(3b) is independently C₅-C₈cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆ haloalkoxy, C₂-C₆ alkenyloxy,C₂-C₆ haloalkenyloxy, C₃-C₆ alkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₉trialkylsilylalkoxy, —CR^(10a)═NOR⁹, —ON═CR^(11a)R^(11b) or-A(CR^(12a)R^(12b))_(n)W.

Embodiment 62

A compound of Embodiment 61 wherein each R^(3b) is independently C₅-C₈cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆ haloalkoxy, C₂-C₆ alkenyloxy,C₂-C₆ haloalkenyloxy, C₃-C₆ alkynyloxy, C₄-C₈ cycloalkylalkoxy,—CR^(10a)═NOR⁹ or -A(CR^(12a)R^(12b))_(n)W.

Embodiment 63

A compound of Embodiment 62 wherein each R^(3b) is independently C₂-C₆alkenyloxy, C₂-C₆ haloalkenyloxy, C₃-C₆ alkynyloxy or-A(CR^(12a)R^(12b))_(n)W.

Embodiment 64

A compound of Embodiment 63 wherein each R^(3b) is-A(CR^(12a)R^(12b))_(n)W.

Embodiment 65

A compound of Formula 1 or any one of Embodiments 1 through 64 whereineach A is O or a direct bond.

Embodiment 66

A compound of Formula 1 or any one of Embodiments 1 through 65 whereineach A is O.

Embodiment 66a

A compound of Formula 1 or any one of Embodiments 1 through 65 whereineach A is a direct bond.

Embodiment 67

A compound of Formula 1 or any one of Embodiments 1 through 66a whereineach W is independently a 3- to 7-membered heterocyclic ring containingring members selected from carbon atoms and 1 to 2 heteroatomsindependently selected from up to 2 O, up to 2 S and up to 2 N atoms,wherein up to 1 carbon atom ring member is C(═O), the ring optionallysubstituted with up to 3 substituents independently selected from R¹³ oncarbon atom ring members and R¹⁴ on nitrogen atom ring members.

Embodiment 68

A compound of Embodiment 67 wherein each W is independently a 3- to6-membered heterocyclic ring containing ring members selected fromcarbon atoms and 1 to 2 heteroatoms independently selected from up to 2O, up to 2 S and up to 2 N atoms, the ring optionally substituted withup to 3 substituents independently selected from R¹³ on carbon atom ringmembers and R¹⁴ on nitrogen atom ring members.

Embodiment 69

A compound of Embodiment 68 wherein each W is independently a 3- to5-membered heterocyclic ring containing ring members selected fromcarbon atoms and 1 to 2 heteroatoms independently selected from up to 2O and up to 2 N atoms, the ring optionally substituted with up to 2substituents independently selected from R¹³ on carbon atom ring membersand R¹⁴ on nitrogen atom ring members.

Embodiment 70

A compound of Embodiment 69 wherein each W is independently a 3- to5-membered heterocyclic ring containing ring members selected fromcarbon atoms and 1 to 2 heteroatoms independently selected from up to 2O and up to 2 N atoms, the ring optionally substituted with up to 2substituents independently selected from R¹³ on carbon atom ringmembers.

Embodiment 70a

A compound of Embodiment 70 wherein each W is independently a 5-memberedheterocyclic ring containing ring members selected from carbon atoms and1 to 2 heteroatoms independently selected from up to 2 O and up to 2 Natoms, the ring optionally substituted with up to 2 substituentsindependently selected from R¹³ on carbon atom ring members.

Embodiment 70b

A compound of Embodiment 70 wherein each W is independently a 3- to5-membered heterocyclic ring containing ring members selected fromcarbon atoms and 1 to 2 heteroatoms independently selected from up to 2O and up to 2 N atoms.

Embodiment 71

A compound of Formula 1 or any one of Embodiments 1 through 70b whereinR⁴ is H, amino, C₂-C₃ alkenyl, C₃-C₄ alkynyl, cyclopropyl, —CH(═O),—S(═O)₂OM, —S(═O)_(m)R¹⁵, —(C═Z)R¹⁶ or OR¹⁷; or C₁-C₃ alkyl or C₁-C₃haloalkyl, each optionally substituted with up to 2 substituentsindependently selected from R¹⁸.

Embodiment 72

A compound of Embodiment 71 wherein R⁴ is H, cyclopropyl, —CH(═O),—S(═O)₂OM, —S(═O)_(m)R¹⁵, —(C═Z)R¹⁶, OR¹⁷, C₁-C₃ alkyl or C₁-C₃haloalkyl.

Embodiment 73

A compound of Embodiment 72 wherein R⁴ is H, —CH(═O), —S(═O)_(m)R¹⁵,—(C═Z)R¹⁶, OR¹⁷, C₁-C₃ alkyl or C₁-C₃ haloalkyl.

Embodiment 74

A compound of Embodiment 73 wherein R⁴ is H, —CH(═O), OR¹⁷, C₁-C₃ alkylor C₁-C₃ haloalkyl.

Embodiment 75

A compound of Embodiment 74 wherein R⁴ is H, —CH(═O) or methoxy.

Embodiment 76

A compound of Embodiment 75 wherein R⁴ is H.

Embodiment 77

A compound of Formula 1 or any one of Embodiments 1 through 76 whereinR^(5a) is H or methyl.

Embodiment 78

A compound of Embodiment 77 wherein R^(5a) is H.

Embodiment 79

A compound of Formula 1 or any one of Embodiments 1 through 78 whereinR^(5b) is H, —CH(═O), C₁-C₃ alkyl, C₁-C₂ haloalkyl, C₂-C₄ cyanoalkyl,C₂-C₃ alkoxyalkyl, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl, C₂-C₄(alkylthio)carbonyl or C₂-C₄ alkoxy(thiocarbonyl).

Embodiment 80

A compound of Embodiment 79 wherein R^(5b) is H, —CH(═O), C₁-C₃ alkyl,C₁-C₂ haloalkyl, C₂-C₄ cyanoalkyl, C₂-C₃ alkoxyalkyl, C₂-C₄alkylcarbonyl or C₂-C₄ alkoxycarbonyl.

Embodiment 81

A compound of Embodiment 80 wherein R^(5b) is H, —CH(═O), methyl,halomethyl, cyanomethyl, methylcarbonyl or methoxycarbonyl.

Embodiment 82

A compound of Embodiment 81 wherein R^(5b) is H.

Embodiment 83

A compound of Formula 1 or any one of Embodiments 1 through 82 whereinR⁶ is H or C₁-C₆ alkyl.

Embodiment 84

A compound of Embodiment 83 wherein R⁶ is H or C₁-C₂ alkyl.

Embodiment 85

A compound of Embodiment 84 wherein R⁶ is H or methyl.

Embodiment 86

A compound of Embodiment 85 wherein R⁶ is H.

Embodiment 87

A compound of Formula 1 or any one of Embodiments 1 through 86 whereinwhen R⁷ is taken alone (i.e. not taken together with R⁸ to form a ring),then R⁷ is H or C₁-C₆ alkyl.

Embodiment 88

A compound of Embodiment 87 wherein R⁷ is H.

Embodiment 89

A compound of Formula 1 or any one of Embodiments 1 through 88 whereinR⁷ is taken alone.

Embodiment 90

A compound of Formula 1 or any one of Embodiments 1 through 89 whereinwhen R⁸ is taken alone (i.e. not taken together with R⁷ to form a ring),then R⁸ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₄-C₈ alkylcycloalkyl.

Embodiment 91

A compound of Embodiment 90 wherein R⁸ is H or C₁-C₆ alkyl.

Embodiment 92

A compound of Embodiment 91 wherein R⁸ is H.

Embodiment 93

A compound of Formula 1 or any one of Embodiments 1 through 92 whereinR⁸ is taken alone.

Embodiment 94

A compound of Formula 1 or any one Embodiments 1 through 93 wherein whenR⁷ and R⁸ are taken together with the nitrogen atom to which they areattached to form a 4- to 7-membered nonaromatic heterocyclic ring, thensaid ring contains ring members, in addition to the connecting nitrogenatom, selected from carbon atoms and up to 1 ring member selected from Oand NR¹⁹.

Embodiment 95

A compound of Embodiment 94 wherein R⁷ and R⁸ are taken together withthe nitrogen atom to which they are attached to form a 5- to 6-memberednonaromatic heterocyclic, containing ring members, in addition to theconnecting nitrogen atom, selected from carbon atoms and up to 1 ringmember selected from O and NR¹⁹ Embodiment 96. A compound of Embodiment95 wherein R⁷ and R⁸ are taken together with the nitrogen atom to whichthey are connected to form a piperidinyl, piperazinyl or morpholinylring.

Embodiment 97

A compound of Formula 1 or any one of Embodiments 1 through 96 whereineach R^(9a) and R^(9b) is independently H or methyl.

Embodiment 98

A compound of Embodiment 97 wherein each R^(9a) and R^(9b) is H.

Embodiment 99

A compound of Formula 1 or any one of Embodiments 1 through 98 whereineach R^(10a) is independently H, methyl or halomethyl.

Embodiment 100

A compound of Embodiment 99 wherein each R^(10a) is H.

Embodiment 101

A compound of Formula 1 or any one of Embodiments 1 through 100 whereineach R^(10b) and R^(10c) is independently H, C₁-C₃ alkyl, C₁-C₃haloalkyl, C₃-C₄ cycloalkyl or C₃-C₄ halocycloalkyl.

Embodiment 102

A compound of Embodiment 101 wherein each R^(10b) and R^(10c) isindependently H, methyl, halomethyl or cyclopropyl.

Embodiment 103

A compound of Formula 1 or any one of Embodiments 1 through 102 whereineach R^(11a) and R^(11b) is independently H, methyl or halomethyl.

Embodiment 104

A compound of Embodiment 103 wherein each R^(11a) and R^(11b) is H.

Embodiment 105

A compound of Formula 1 or any one of Embodiments 1 through 104 whereineach R^(12a) is independently H, cyano, halogen or methyl.

Embodiment 106

A compound of Embodiment 105 wherein each R^(12a) is independently H ormethyl.

Embodiment 107

A compound of Embodiment 106 wherein each R^(12a) is H.

Embodiment 108

A compound of Formula 1 or any one of Embodiments 1 through 107 whereineach R^(12b) is independently H or methyl.

Embodiment 109

A compound of Embodiment 108 wherein each R^(12b) is H.

Embodiment 110

A compound of Formula 1 or any one of Embodiments 1 through 109 whereineach R¹³ is independently cyano, halogen, methyl, halomethyl, methoxy orhalomethoxy.

Embodiment 111

A compound of Embodiment 110 wherein each R¹³ is independently halogen,methyl, halomethyl or methoxy.

Embodiment 112

A compound of Embodiment 111 wherein each R¹³ is methyl.

Embodiment 113

A compound of Formula 1 or any one of Embodiments 1 through 112 whereineach R¹⁴ is independently methyl or methoxy.

Embodiment 114

A compound of Formula 1 or any one of Embodiments 1 through 113 whereinR¹⁵ is methyl or halomethyl.

Embodiment 115

A compound of Formula 1 or any one of Embodiments 1 through 114 whereinR¹⁶ is C₁-C₆ alkyl, C₁-C₆ alkoxy or C₁-C₆ alkylthio.

Embodiment 116

A compound of Embodiment 115 wherein R¹⁶ is methyl, ethyl, methoxy,ethoxy, methylthio or ethylthio.

Embodiment 117

A compound of Embodiment 116 wherein R¹⁶ is methyl, methoxy ormethylthio.

Embodiment 118

A compound of Formula 1 or any one of Embodiments 1 through 117 whereinR¹⁷ is H, —CH(═O), cyclopropyl, —S(═O)₂OM or —(C═Z)R²⁰; or C₁-C₃ alkylor C₁-C₃ haloalkyl, each optionally substituted with up to 2substituents independently selected from R²¹.

Embodiment 119

A compound of Formula 1 or any one of Embodiments 1 through 118 whereineach R¹⁸ and R²¹ is independently cyano, C₃-C₆ cycloalkyl or C₁-C₃alkoxy.

Embodiment 120

A compound of Embodiment 119 wherein each R¹⁸ and R²¹ is independentlycyano, cyclopropyl or methoxy.

Embodiment 121

A compound of Embodiment 120 wherein each R¹⁸ and R²¹ is independentlycyclopropyl or methoxy.

Embodiment 122

A compound of Formula 1 or any one of Embodiments 1 through 121 whereinR¹⁹ is H or CH₃.

Embodiment 123

A compound of Embodiment 122 wherein R¹⁹ is CH₃.

Embodiment 124

A compound of Formula 1 or any one of Embodiments 1 through 123 whereinR²⁰ is C₁-C₆ alkyl, C₁-C₆ alkoxy or C₁-C₆ alkylthio.

Embodiment 125

A compound of Embodiment 124 wherein R²⁰ is methyl, ethyl, methoxy,ethoxy, methylthio or ethylthio.

Embodiment 126

A compound of Embodiment 125 wherein R²⁰ is methyl, methoxy ormethylthio.

Embodiment 127

A compound of Formula 1 or any one of Embodiments 1 through 126 whereineach U is independently O or NR²².

Embodiment 128

A compound of Embodiment 127 wherein each U is independently O or NH.

Embodiment 129

A compound of Formula 1 or any one of Embodiments 1 through 128 whereineach V is C₂-C₄ alkylene.

Embodiment 130

A compound of Formula 1 or any one of Embodiments 1 through 129 whereineach T is independently NR^(23a)R^(23b) or OR²⁴.

Embodiment 131

A compound of Formula 1 or any one of Embodiments 1 through 130 whereineach R^(23a) and R^(23b) is independently H, C₁-C₆ alkyl or C₁-C₆haloalkyl.

Embodiment 132

A compound of Embodiment 131 wherein each R^(23a) and R^(23b) isindependently H, methyl or halomethyl.

Embodiment 133

A compound of Formula 1 or any one of Embodiments 1 through 132 whereineach R²⁴ is independently H, C₁-C₆ alkyl or C₁-C₆ haloalkyl.

Embodiment 134

A compound of Embodiment 133 wherein each R²⁴ is methyl.

Embodiment 135

A compound of Formula 1 or any one of Embodiments 1 through 134 whereinZ is O.

Embodiment 136

A compound of Formula 1 or any one of Embodiments 1 through 135 whereinM is K or Na.

Embodiment 137

A compound of Formula 1 or any one of Embodiments 1 through 136 whereinm is 0.

Embodiment 138

A compound of Formula 1 or any one of Embodiments 1 through 137 whereineach n is 3.

Embodiment 139

A compound of Formula 1 or any one of Embodiments 1 through 137 whereineach n is independently 0, 1 or 2.

Embodiment 140

A compound of Formula 1 or any one of Embodiments 1 through 137 whereineach n is independently 1, 2 or 3.

Embodiment 141

A compound of Embodiment 139 wherein each n is independently 0 or 1.

Embodiment 142

A compound of Embodiments 139 through 141 wherein each n is 1.

Embodiment 143

A compound of Embodiments 139 or 141 wherein each n is 0.

Embodiments of this invention, including Embodiments 1-143 above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1 but also to the starting compoundsand intermediate compounds useful for preparing the compounds of Formula1 unless further defined in the Embodiments. In addition, embodiments ofthis invention, including Embodiments 1-143 above as well as any otherembodiments described herein, and any combination thereof, pertain tothe compositions and methods of the present invention. Combinations ofEmbodiments 1-143 are illustrated by:

Embodiment A

A compound of Formula 1 wherein

-   -   Q¹ is a phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl        ring, each ring optionally substituted with up to 3 substituents        independently selected from R^(3a) and R^(3b);    -   Q² is a phenyl, pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl        ring, each ring optionally substituted with up to 3 substituents        independently selected from R^(3a) and R^(3b);    -   X is O, NR⁴ or CHOR^(5b);    -   R¹ is H, cyano, halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₄        alkenyl, C₂-C₄ alkynyl, cyclopropyl, C₂-C₄ alkoxyalkyl, C₁-C₃        alkoxy, C₁-C₃ haloalkoxy, —C(═O)OR⁶ or —C(═O)NR⁷R⁸;    -   R^(1a) is H;    -   R² is Br, Cl, I or C₁-C₂ alkyl;    -   each R^(3a) is independently amino, cyano, halogen, C₁-C₃ alkyl,        C₁-C₃ haloalkyl, C₂-C₄ alkenyl, C₃-C₄ cycloalkyl, C₄-C₆        cycloalkylalkyl, C₄-C₆ alkylcycloalkyl, C₁-C₃ alkylthio, C₁-C₃        alkylsulfinyl, C₁-C₃ alkylsulfonyl, C₁-C₃ alkoxy, C₁-C₃        haloalkoxy, C₃-C₆ cycloalkoxy, C₁-C₃ alkylsulfonyloxy, C₂-C₄        alkylcarbonyloxy, C₂-C₄ alkylcarbonyl, C₁-C₃ alkylamino, C₂-C₄        dialkylamino, C₂-C₄ alkylcarbonylamino, —CH(═O), —NHCH(═O),        —SF₅, —SC≡N or —U—V-T;    -   each R^(3b) is independently C₂-C₄ haloalkenyl, C₅-C₈        cycloalkylalkenyl, C₅-C₈ cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆        haloalkoxy, C₂-C₆ alkenyloxy, C₂-C₆ haloalkenyloxy, C₃-C₆        alkynyloxy, C₃-C₆ haloalkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₆        alkylsulfonyloxy, C₄-C₆ haloalkylsulfonyloxy, C₃-C₉        trialkylsilyl, C₄-C₉ trialkylsilylalkyl, C₄-C₉        trialkylsilylalkoxy, —C(═S)NR^(9a)R^(9b), —CR^(10a)═NOR^(10b),        —ON═CR^(11a)R^(11b) or -A(CR^(12a)R^(12b))_(n)W;    -   each W is independently a 3- to 7-membered heterocyclic ring        containing ring members selected from carbon atoms and 1 to 2        heteroatoms independently selected from up to 2 O, up to 2 S and        up to 2 N atoms, wherein up to 1 carbon atom ring member is        C(═O), the ring optionally substituted with up to 3 substituents        independently selected from R¹³ on carbon atom ring members and        R¹⁴ on nitrogen atom ring members;    -   R⁴ is H, cyclopropyl, —CH(═O), —S(═O)₂OM, —S(═O)_(m)R¹⁵,        —(C═Z)R¹⁶, OR¹⁷, C₁-C₃ alkyl or C₁-C₃ haloalkyl;    -   R^(5b) is H, —CH(═O), C₁-C₃ alkyl, C₁-C₂ haloalkyl, C₂-C₄        cyanoalkyl, C₂-C₃ alkoxyalkyl, C₂-C₄ alkylcarbonyl or C₂-C₄        alkoxycarbonyl;    -   R⁶ is H or methyl;    -   R⁷ is H or C₁-C₆ alkyl;    -   R⁸ is H, C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₄-C₈ alkylcycloalkyl;    -   each R^(9a) and R^(9b) is independently H or methyl;    -   each R^(10a) is independently H, methyl or halomethyl;    -   each R^(10b) is independently H, C₁-C₃ alkyl, C₁-C₃ haloalkyl,        C₃-C₄ cycloalkyl or C₃-C₄ halocycloalkyl;    -   each R^(11a) and R^(11b) is independently H, methyl or        halomethyl;    -   each R^(12a) is independently H, cyano, halogen or methyl;    -   each R^(12b) is independently H or methyl;    -   each R¹³ is independently halogen, methyl, halomethyl or        methoxy;    -   each R¹⁴ is independently methyl or methoxy;    -   R¹⁵ is methyl or halomethyl;    -   R¹⁶ is methyl, ethyl, methoxy, ethoxy, methylthio or ethylthio;    -   R¹⁷ is H, —CH(═O), cyclopropyl, —S(═O)₂OM or —(C═Z)R²⁰; or C₁-C₃        alkyl or C₁-C₃ haloalkyl, each optionally substituted with up to        2 substituents independently selected from R²¹;    -   R²⁰ is methyl, methoxy or methylthio;    -   each U is independently O or NR²²;    -   each V is independently C₂-C₄ alkylene;    -   each T is independently NR^(23a)R^(23b) or OR²⁴;    -   each R^(23a) and R^(23b) is independently H, C₁-C₆ alkyl or        C₁-C₆ haloalkyl;    -   each R²⁴ is independently H, C₁-C₆ alkyl or C₁-C₆ haloalkyl; and        Z is O.

Embodiment B

A compound of Embodiment A wherein

-   -   Q¹ is a phenyl ring optionally substituted with up to 3        substituents independently selected from R^(3a) and from R^(3b);    -   Q² is a phenyl ring optionally substituted with up to 3        substituents independently selected from R^(3a) and R^(3b);    -   R¹ is H, cyano, halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₄        alkoxyalkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkoxy;    -   each R^(3a) is independently cyano, halogen, methyl, halomethyl,        cyclopropyl, methylthio, methoxy, methylsulfonyloxy,        methylcarbonyloxy, methylcarbonyl or —U—V-T;    -   each R^(3b) is independently C₅-C₈ cycloalkylalkenyl, C₅-C₈        cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆ haloalkoxy, C₂-C₆        alkenyloxy, C₂-C₆ haloalkenyloxy, C₃-C₆ alkynyloxy, C₃-C₆        haloalkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₆ alkylsulfonyloxy,        C₄-C₆ haloalkylsulfonyloxy, C₄-C₉ trialkylsilylalkoxy,        —C(═S)NR^(9a)R^(9b), —CR^(10a)═NOR^(10b), —ON═CR^(11a)R^(11b) or        -A(CR^(12a)R^(12b))_(n)W;    -   each W is independently a 3- to 5-membered heterocyclic ring        containing ring members selected from carbon atoms and 1 to 2        heteroatoms independently selected from up to 2 O and up to 2 N        atoms, the ring optionally substituted with up to 2 substituents        independently selected from R¹³ on carbon atom ring members and        R¹⁴ on nitrogen atom ring members;    -   R⁴ is H, —CH(═O) or methoxy;    -   R^(5b) is H, —CH(═O), methyl, halomethyl, cyanomethyl,        methylcarbonyl or methoxycarbonyl;    -   each R^(12a) is independently H or methyl;    -   each R^(12b) is H; and    -   each U is independently O or NH.

Embodiment C

A compound of Embodiment B wherein

-   -   X is NR⁴ or CHOR^(5b);    -   R¹ is H, halogen or C₁-C₃ alkyl;    -   R² is Br, Cl or methyl;    -   each R^(3a) is independently cyano, halogen or methoxy;    -   each R^(3b) is independently C₅-C₈ cycloalkylalkynyl, C₄-C₆        alkoxy, C₄-C₆ haloalkoxy, C₂-C₆ alkenyloxy, C₂-C₆        haloalkenyloxy, C₃-C₆ alkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₉        trialkylsilylalkoxy, —CR^(10a)═NOR⁹, —ON═CR^(11a)R^(11b) or        -A(CR^(12a)R^(12b))_(n)W;    -   R⁴ is H;    -   R^(5b) is H;    -   each R^(10a) is H;    -   each R^(10b) is independently H, methyl, halomethyl or        cyclopropyl; and    -   each R^(12a) is H.

Embodiment D

A compound of Embodiment C wherein

-   -   Q¹ is a phenyl ring optionally substituted with up to 2        substituents independently selected from R^(3a) and substituted        with 1 substituent selected from R^(3b);    -   Q² is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a);    -   R¹ is H;    -   R² is methyl; and    -   each R^(3a) is independently Br, Cl or F.

Embodiment E

A compound of Formula 1 wherein

-   -   Q¹ is a phenyl ring substituted at the 2-, 4- and 6-positions        with substituents independently selected from R^(3a) and R^(3b);        or a phenyl ring substituted at the 2- and 4-positions with        substituents independently selected from R^(3a) and R^(3b); or a        phenyl ring substituted at the 2- and 6-positions with        substituents independently selected from R^(3a) and R^(3b).    -   Q² is a phenyl ring substituted at the 2-, 4- and 6-positions        with substituents independently selected from R^(3a) and R^(3b);        or a phenyl ring substituted at the 2- and 4-positions with        substituents independently selected from R^(3a) and R^(3b); or a        phenyl ring substituted at the 2- and 6-positions with        substituents independently selected from R^(3a) and R^(3b).    -   X is NR⁴ or CHOR^(5b);    -   R¹ is H or methyl;    -   R^(1a) is H;    -   R² is Br, Cl or methyl;    -   each R^(3a) is independently cyano, halogen or methoxy;    -   each R^(3b) is independently C₅-C₈ cycloalkylalkynyl, C₄-C₆        alkoxy, C₄-C₆ haloalkoxy, C₂-C₆ alkenyloxy, C₂-C₆        haloalkenyloxy, C₃-C₆ alkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₉        trialkylsilylalkoxy, —C(═S)NR^(9a)R^(9b), —CR^(10a)═NOR^(10b),        —ON═CR^(11a)R^(11b) or -A(CR^(12a)R^(12b))_(n)W;    -   each W is independently a 3- to 5-membered heterocyclic ring        containing ring members selected from carbon atoms and 1 to 2        heteroatoms independently selected from up to 2 O and up to 2 N        atoms, the ring optionally substituted with up to 2 substituents        independently selected from R¹³ on carbon atom ring members;    -   R⁴ is H;    -   R^(5b) is H;    -   each R^(9a) and R^(9b) is independently H or methyl;    -   each R^(10a) is independently H, methyl or halomethyl;    -   each R^(10b) is independently H, C₁-C₃ alkyl, C₁-C₃ haloalkyl,        C₃-C₄ cycloalkyl or C₃-C₄ halocycloalkyl;    -   each R^(11a) and R^(11b) is independently H, methyl or        halomethyl;    -   each R^(12a) is independently H, cyano, halogen or methyl;    -   each R^(12b) is independently H or methyl; and each R¹³ is        independently halogen, methyl, halomethyl or methoxy.

Embodiment E

A compound of Embodiment E wherein

-   -   Q¹ is a phenyl ring substituted with 2 substituents        independently selected from R^(3a) and 1 substituent selected        from R^(3b);    -   Q² is a phenyl ring substituted with 1 to 3 substituents        independently selected from R^(3a);    -   X is CHOR^(5b);    -   R¹ is H;    -   R² is methyl;    -   each R^(3a) is independently Br, Cl or F;    -   R^(3b) is C₅-C₈ cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆        haloalkoxy, C₂-C₆ alkenyloxy, C₂-C₆ haloalkenyloxy, C₃-C₆        alkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₉ trialkylsilylalkoxy,        —CR^(10a)═NOR⁹, —ON═CR^(11a)R^(11b) or -A(CR^(12a)R^(12b))_(n)W;    -   W is a 3- to 5-membered heterocyclic ring containing ring        members selected from carbon atoms and 1 to 2 heteroatoms        independently selected from up to 2 O and up to 2 N atoms;    -   R^(12a) is H;    -   R^(12b) is H; and    -   n is 0, 1 or 2.

Embodiment F

A compound of Embodiment E wherein

-   -   Q¹ is a phenyl ring substituted with 2 substituents        independently selected from R^(3a) which are attached at the 2-        and 6-positions and 1 substituent selected from R^(3b) which is        attached at the 4-position;    -   Q² is a phenyl ring substituted with 2 substituents        independently selected from R^(3a) which are attached at the 2-        and 6-positions; or a phenyl ring substituted with 2        substituents independently selected from R^(3a) which    -   R^(3b) is C₅-C₈ cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆        haloalkoxy, C₂-C₆ alkenyloxy, C₂-C₆ haloalkenyloxy, C₃-C₆        alkynyloxy, C₄-C₈ cycloalkylalkoxy, —CR^(10a)═NOR⁹ or        -A(CR^(12a)R^(12b))_(n)W.

Specific embodiments include compounds of Formula 1 selected from thegroup consisting of:

-   α-(2-chloro-4-fluorophenyl)-5-[2,6-difluoro-4-(1H-pyrazol-1-yl)phenyl]-1,3-dimethyl-1H-pyrazole-4-methanol;-   α-(2-chloro-4-fluorophenyl)-5-[4-(2-cyclopropylethynyl)-2,6-difluorophenyl]-1,3-dimethyl-1H-pyrazole-4-methanol;-   α-(2-chloro-4-fluorophenyl)-5-[4-(cyclopropylmethoxy)-2,    6-difluorophenyl]-1,3-dimethyl-1H-pyrazole-4-methanol.

One or more of the following methods and variations as described inSchemes 1-22 can be used to prepare the compounds of Formula 1. Thedefinitions of Q¹, Q², X, R¹, R^(1a), R², R^(3a), R^(3b), R⁴ and R^(5a)in the compounds of Formulae 1-35 below are as defined above in theSummary of the Invention unless otherwise noted. Formulae 1a-1k, 1m and1n are various subsets of Formula 1. Substituents for each subsetformula are as defined for its parent formula unless otherwise noted.

Compounds of Formula 1 can be prepared as shown in Scheme 1. In thismethod a compound of Formula 2 is first treated with an organometallicagent of Formula 3 such as an alkyl lithium base (e.g., n-butyllithium,s-butyllithium or lithium diisopropylamide) or a Grignard reagent in asolvent such as toluene, diethyl ether, tetrahydrofuran ordimethoxymethane at temperatures ranging from about −78° C. to ambienttemperature. Anions of Formula 2a are then contacted with anelectrophile of Formula 4, 5 or 6. The use and choice of an appropriateelectrophile will depend on the desired compound of Formula 1 and willbe apparent to one skilled in chemical synthesis. For example,chlorosulfides of formula Q²SCl or disulfies formula of Q²S—S-Q² (i.e.Formula 4) provide compounds of Formula 1a (i.e. Formula 1 wherein X isS), aldehydes of the formula Q²CHO (i.e. Formula 5) provide compounds ofFormula 1b (i.e. Formula 1 wherein X is CH(OH)) and nitrosobenzenes offormula Q²-N═O (i.e. Formula 6) provide compounds of Formula 1c (i.e.Formula 1 wherein X is N(OH)). There are a wide-variety of generalmethods described in the synthetic literature for metalation/alkylationreactions which can be readily adapted to prepare compounds of thepresent invention; see, for example Inorganic Chemistry 2012, 51(17),9385-9394 and PCT Publication WO 2010/030922 A1 (Example 4, Step D,Example 6 and Example 9, Step E).

Electrophiles of Formulae 4, 5 and 6 are commercially available and canbe prepared by methods known in the art. Compounds of Formula 2 areknown and can be prepared by the method disclosed in Scheme 6 below, andby a variety of methods disclosed in the chemical literature.

Alternatively, as shown in Scheme 2, compounds of Formula 1b (i.e.Formula 1 wherein X is C(OH)) can be prepared from the correspondingketone compounds of Formula 7 using standard reduction techniques.Typical reaction conditions involve contacting a compound of Formula 7with a boron-based reducing agent such as sodium borohydride or sodiumtriacetoxyborohydride in a solvent such as methanol, ethanol ortetrahydrofuran. Other techniques known to those skilled in the art mayalso be employed. For relevant references, see, for example, Journal ofthe American Chemical Society 2006, 128, 9998-9999 and PCT PublicationWO 2010/030922 A1 (Examples 8 and 11).

As shown in Scheme 3, compounds of Formula 7 can also be treated withalkylmagnesium halides to provide compounds of Formula 1d (i.e. Formula1 wherein X is C(OH)R^(5a) and R^(5a) is C₁-C₆ alkyl). Typically thereaction is run in presence of zinc chloride and in a solvent such asdiethyl ether or tetrahydrofuran at temperatures from about 0-100° C.For reaction conditions; see, for example, Journal of the AmericanChemical Society 2006, 128, 9998-9999.

As shown in Scheme 4, intermediates of Formula 7 can be prepared using amethod analogous to Scheme 1, wherein anions of Formula 2a are treatedwith benzoyl chlorides of formula Q¹C(═O)Cl (i.e. Formula 8) orbenzamides of formula Q¹C(═O)N(Me)OMe (i.e. Formula 9) to providecompounds of Formula 7. In cases where the electrophile is Q¹C(═O)Cl,the addition of a second organometallic reagent such as zinc chloride,zinc bromide or a monovalent copper salt such as copper(I) iodide orcopper(I) cyanide before the addition of the electrophile promotesreactivity. For a related reference, see, for example, Journal ofMedicinal Chemistry 1986, 29(9), 1628-11637.

In an alternate approach, intermediates of Formula 7 can also beprepared from compounds of Formula 10 using Friedel-Crafts acylationconditions as illustrated in Scheme 5. In this method, a compound ofFormula 10 is contacted with an acid chloride of Formula 11 in thepresence of a Lewis acid (e.g., aluminum chloride, boron trifluoridediethyl etherate or tin tetrachloride) in a solvent such asdichloromethane, tetrachloroethane or nitrobenzene, at temperaturesranging between about 0 to 200° C. In the present disclosure, Example 1,Step D illustrates the method of Scheme 5.

As shown in Scheme 6, intermediates of Formula 2 are readily preparedfrom compounds of Formula 10 by treatment with a halogenating agent.Suitable halogenating agents for this method include N-bromosuccinimide(NBS), N-iodosuccinimide (NIS), bromine, sodium bromite, thionylchloride, oxalyl chloride, phenylphosphonic dichloride or phosgene.Particularly useful is N-bromosuccinimide (NBS) and N-iodosuccinimide(NIS). Suitable solvents for this reaction include, for example,N,N-dimethylformamide, N,N-dimethylacetamide, dichloromethane,chloroform, chlorobutane, benzene, xylenes, chlorobenzene,tetrahydrofuran, p-dioxane, acetonitrile, and the like. Optionally, abase such as sodium carbonate, triethylamine, pyridine,N,N-dimethylaniline, and the like can be added. Typical reactiontemperatures range from about ambient temperature to 200° C. Forrepresentative procedures, see, for example, Czarnocki et al., SynthesisCommunications 2007, 37(1), 137-147, and PCT Publication WO 2010/030922A1 (Example 3, Step C, Example 4, Step C and Example 9, Step D).

As shown in Scheme 7, intermediates of Formula 10 can be prepared byreaction of a 5-bromo or 5-iodo pyrazole of Formula 12 undertransition-metal-catalyzed cross-coupling reaction conditions. In thismethod reaction of a pyrazole of Formula 12 is contacted with a compoundof formula Q¹-M² (i.e. Formula 13) in the presence of a suitablepalladium, copper or nickel catalyst, to provide a compound of Formula10. Suitable compounds of formula Q¹-M² include organoboronic acids(e.g., M² is B(OH)₂), organoboronic esters (e.g., M² isB(—OC(CH₃)₂C(CH₃)₂O—)), organotrifluoroborates (e.g., M² is BF₃K),organotin reagents (e.g., M² is Sn(n-Bu)₃, Sn(Me)₃), Grignard reagents(e.g., M² is MgBr or MgCl) or organozinc reagents (e.g., M² is ZnBr orZnCl). Suitable metal catalysts include, but are not limited to:palladium(II) acetate, palladium(II) chloride,tetrakis(triphenylphosphine)-palladium(0),bis(triphenylphosphine)palladium(II) dichloride,dichloro[1,1′-bis(diphenyl-phosphino)ferrocene]palladium(II),bis(triphenylphosphine)dichloronickel(II) and copper(I) salts (e.g.,copper(I) iodide, copper(I) bromide, copper(I) chloride, copper(I)cyanide or copper(I) triflate). Optimal conditions for each reactionwill depend on the catalyst used and the counterion attached to thecoupling reagent (i.e. M²), as is understood by one skilled in the art.In some cases the addition of a ligand such as a substituted phosphineor a substituted bisphosphinoalkane promotes reactivity. Also, thepresence of a base such as an alkali carbonate, tertiary amine or alkalifluoride may be necessary for some reactions involving organoboronreagents of the formula Q¹-M². For reviews of this type of reaction see:E. Negishi, Handbook of Organopalladium Chemistry for Organic Synthesis,John Wiley and Sons, Inc., New York, 2002; N. Miyaura, Cross-CouplingReactions: A Practical Guide, Springer, New York, 2002; H. C. Brown etal., Organic Synthesis via Boranes, Vol. 3, Aldrich Chemical Co.,Milwaukee, Wis., 2002; Suzuki et al., Chemical Review 1995, 95,2457-2483 and Accounts of Chemical Research 2007, 40, 275-286. Forrepresentative procedures, see, for example, PCT Publication WO2010/030922 A1 (Example 9, Step C).

Alternatively, as shown in Scheme 8, intermediates of Formula 10 can beprepared by cyclization of enones of Formula 14 with an appropriatelysubstituted hydrazine of formula NH₂NH—CHR¹R^(1a) (i.e. Formula 15) andsubsequent oxidation of pyrazolines of Formula 16. Useful oxidizingreagents include bromine (for conditions see, for example, IndianJournal of Heterocyclic Chemistry, 2001, 11(1), 21-26), elementalsulfur, manganese dioxide, 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ),chloranil (for conditions see, for example, Russian Journal of OrganicChemistry 2006, 42(8), 1113-1119) and oxygen optionally in the presenceof a metal catalyst such as cobalt acetate (for conditions see, forexample, Tetrahedron 2006, 62(11), 2492-2496 and Chinese ChemicalLetters 2008, 19(9), 1013-1016). Useful solvents for this reactioninclude N,N-dimethylformamide, tetrahydrofuran, toluene, water,dichloromethane, tetrachloroethane, and mixtures of these or similarsolvents, at temperatures from ambient to 200° C. The reaction ofhydrazines with enones and the preparation of the enones is well-knownin the art, see, for example, Synthesis 2012, 44, 2401-2407 and PCTPublication WO 2010/030922 A1 (Example 4, Step B). Also, in the presentdisclosure, Example 1, Step C illustrates the method of Scheme 8. Scheme8

As shown in Scheme 9, compounds of Formula 12 can be prepared byalkylation of corresponding pyrazoles of Formula 17 with an alkylatingagent of formula CHR¹R^(1a)-L² (i.e. Formula 18) wherein L² is a leavinggroup such as halogen or (halo)alkylsulfonate (e.g., Cl, Br, I,p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate).General procedures for alkylations of this type are well-known in theart and can be readily adapted to prepare compounds of the presentinvention. Particularly useful alkylating agents for preparing compoundsof Formula 12 (wherein R¹ and R^(1a)) are H are diazomethane oriodomethane using general procedures known in the art, such as thosedescribed in Tetrahedron Letters 2009, 50(49), 6783-6786 and PCTPublication WO 2010/030922 A1 (Example 9, Step B).

Starting compounds of Formula 17 are known and can be prepared by avariety of methods disclosed in the chemical literature, see, forexample, PCT Publication WO 2010/030922 A1 (Example 9, Step A).

As shown in Scheme 10, Compounds of Formula 1 wherein X is O, S or NR⁴can be prepared by reacting compounds of Formula 19 (e.g.,4-hydroxypyrazoles for X being O, 4-mercaptopyrazoles for X being S and4-aminopyrazoles for X being NR⁴) with compounds of Formula 20 where L²is a leaving group such as halogen or (halo)alkylsulfonate (e.g., Cl,Br, I, p-toluenesulfonate, methanesulfonate ortrifluoromethanesulfonate), optionally in the presence of a metalcatalyst, and generally in the presence of a base and a polar aproticsolvent such as N,N-dimethylformamide or dimethyl sulfoxide. Compoundsof Formula 20 wherein Q² is a phenyl ring substituted withelectron-withdrawing substituents react with compounds of Formula 19 bydirect displacement of the leaving group L² to provide compounds ofFormula 1. Typically for these types of reactions L² is F or Cl.Compounds of Formula 20 wherein Q² is a phenyl ring not substituted withan electron-withdrawing substituent, or in general, to improve reactionrate, yield or product purity, the use of a metal catalyst in amountsranging from catalytic up to superstoichiometric can facilitate thedesired reaction. Typically for these conditions, L² is Br or I or asulfonate such as —OS(O)₂CF₃ or —OS(O)₂(CF₂)₃CF₃. For example, thereaction can be run in the presence of a metal catalyst such as coppersalt complexes (e.g., CuI with N,N′-dimethylethylenediamine, proline orbipyridyl), or palladium complexes (e.g.,tris(dibenzylideneacetone)dipalladium(0)) or palladium salts (e.g.,palladium acetate) with ligands such as4,5-bis(diphenylphosphino)-9,9-dimethylxanthene,2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl or2,2′-bis-(diphenylphosphino)1,1′-binaphthalene, and with a base such aspotassium carbonate, cesium carbonate, sodium phenoxide or sodiumtert-butoxide, in a solvent such as N,N-dimethylformamide,1,2-dimethoxyethane, dimethyl sulfoxide, 1,4-dioxane or toluene,optionally containing an alcohol such as ethanol. For representativeprocedures, see, for example, Archives of Pharmacal Research 2002,25(6), 781-785 and PCT Publication WO 2010/030922 A1 (Example 1, Step Cand Example 2, Step G).

Compounds of Formula 19 are commercially available and their preparationis known in the art, see, for example, Journal für Praktische Chemie(Leipzig) 1911, 83, 171-182, Journal of the American Chemical Society1954, 76, 501-503 and PCT Publication WO 2010/030922 A1 (Example 1,Steps A through B).

As shown in Scheme 11, compounds of Formula 1 can also be prepared byreaction of a 5-bromo or 5-iodo pyrazole of Formula 21 with anorganometallic compound of Formula 22 under transition-metal-catalyzedcross-coupling reaction conditions analogous to those described forScheme 7. Reaction of a pyrazole of Formula 21 with a boronic acid,trialkyltin or an organomagnesium reagent of Formula 22 in the presenceof a palladium or nickel catalyst and optionally a ligand (e.g.,triphenylphosphine, dibenzylideneacetone,dicyclohexyl(2′,6′-dimethoxy[1,1′-biphenyl]-2-yl)phosphine) and a baseaffords a compound of Formula 1. For example, a compound of Formula 22wherein M³ is B(OH)₂, B(OC(CH₃)₂C(CH₃)₂₀)) or B(O-i-Pr)₃ Li reacts witha 5-bromo- or 5-iodopyrazole of Formula 21 in the presence ofdichlorobis(triphenylphosphine) palladium(II) and an aqueous base suchas sodium carbonate or potassium hydroxide, in solvents such as1,4-dioxane, 1,2-dimethoxyethane, toluene or ethyl alcohol, or underanhydrous conditions with the use of a ligand such as phosphine oxide orphosphite ligand (e.g., diphenylphosphine oxide) and potassium fluoridein a solvent such as 1,4-dioxane to provide a compound of Formula 1. Forreferences, see Angewandte Chemie, International Edition 2008, 47(25),4695-4698 and PCT Publication WO 2010/030922 A1 (Example 3, Step D).

Compounds of Formula 21 can be prepared via halogenation methodsanalogous to those described for Scheme 6 (for conditions see PCTPublication WO 2010/030922 A1, Example 3, Step C).

Compounds of Formula 1 can be subjected to various nucleophilic,metalation and oxidation reactions to add substituents or modifyexisting substituents, and thus provide other functionalized compoundsof Formula 1. For example, as shown in Scheme 12, compounds of Formula1e (i.e. Formula 1 wherein X in NR⁴ and R⁴ is other than H) can beprepared by reacting corresponding compounds of Formula 1f (i.e. Formula1 wherein X is NH) with an electrophile comprising R⁴ (i.e. Formula 23)typically in the presence of a base such as sodium hydride and a polarsolvent such as N,N-dimethylformamide. In this context the expression“electrophile comprising R⁴” means a chemical compound capable oftransferring an R⁴ moiety to a nucleophile (such as the nitrogen atom inFormula 1f). Often electrophiles comprising R⁴ have the formula R⁴L³wherein L³ is a nucleofuge (i.e. leaving group in nucleophilicreactions). Typical nucleofuges include halogens (e.g., Cl, Br, I) andsulfonates (e.g., OS(O)₂CH₃, OS(O)₂CF₃, OS(O)₂-(4-CH₃-Ph)). However,some electrophiles comprising R⁴ do not comprise a nucleofuge; anexample is sulfur trioxide (SO₃) which, after deprotonation (such as bya base of the formula M⁺H⁻ wherein M⁺ is a cation) of the nitrogen atomin Formula 1f, can bond to the nitrogen atom as a —S(═O)₂OM substituent.

In another example, as shown in Scheme 13, a fluoro can be introduced atthe 3-position of the pyrazole ring by treating compounds Formula 1h(i.e. Formula 1 wherein R² is chlorine) with potassium fluoride orcesium fluoride in presence of a solvent such as dimethyl sulfoxide orN,N-dimethylformamide at about 0-25° C. for about 30 minutes to 4 h,using procedures such as those described in Zhurnal Organicheskoi Khimii1983, 19, 2164-2173.

Additionally, as shown in Scheme 14, sulfoxides and sulfones of Formula1i (i.e. Formula 1 wherein X is S(═O)_(m) and m is 1 or 2) can beprepared by oxidation of compounds of Formula 1a (i.e. Formula 1 whereinX is S). Typically, an oxidizing agent in an amount of about 1 to 4equivalents, depending on the oxidation state of the desired product, isadded to a mixture of a compound of Formula 1a and a solvent. Usefuloxidizing agents include Oxone® (potassium peroxymonosulfate), potassiumpermanganate, hydrogen peroxide, sodium periodate, peracetic acid and3-chloroperbenzoic acid. The solvent is selected with regard to theoxidizing agent employed. Aqueous ethanol or aqueous acetone ispreferably used with potassium peroxymonosulfate, and dichloromethane isgenerally preferable with 3-chloroperbenzoic acid. Useful reactiontemperatures typically range from about −78 to 90° C. Oxidationreactions of this type are described in J. Agric. Food Chem. 1984, 32,221-226 and J. Agric. Food Chem. 2008, 56, 10160-10167.

Furthermore, for some compounds of Formula 1 the R^(3a) and/or R^(3b)substituents attached to Q¹ and Q² may be more conveniently incorporatedafter forming the central pyrazole ring with Q¹ and Q² already attached.For example, compounds of Formula 1j (i.e. Formula 1 wherein Q¹ isphenyl and R^(3b) is alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, andthe like) can be prepared by reacting hydroxyphenyl derivatives ofFormula 24 with compounds of formula 25 wherein L² is a suitable leavinggroup such as halogen or (halo)alkylsulfonate (e.g., Cl, Br, I,p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate), inthe presence of a base such as potassium carbonate, potassiumtert-butoxide, sodium hydride or triethylamine, and in an aproticsolvent such as N,N-dimethylformamide, acetonitrile, dimethylsulfoxideor tetrahydrofuran at a temperature between about −20 and 150° C. Thisreaction works particularly well when the hydroxy group (—OH) is in the4-position of the phenyl ring of Formula 24 and at least one of thesubstituents R^(3a) is an electron withdrawing group such as fluoride.For a reference describing the general method of Scheme 15 see Chemical& Pharmaceutical Bulletin 2008, 56(8), 1126-1137.

The resulting alkoxy compounds of Formula 1j can themselves be used infurther reactions to prepare compounds of Formula 1 wherein R^(3a) is—U—V-T (see, for example, PCT Publication WO 2007/149448 A2).

As shown in Scheme 16, hydroxyphenyl derivatives of Formula 24 can beprepared from boronic acids or esters of Formula 26 via oxidativehydroxylation. A variety of oxidizing agents can be used in this method,particularly useful reagents include hydrogen peroxide and N-oxides suchas N,N,4-trimethylbenzenamine N-oxide according to procedures reportedin Tetrahedron Letters 2012, 53, 6004-6007 and Organic Letters 2012,14(13), 3494-3497.

As shown in Scheme 17, the intermediate boronic acids or esters ofFormula 26 can be prepared by contacting compounds of Formula 27 whereinL³ is Cl, Br, I or a triflate group with a boronic acid or ester ofFormula 28. The reaction is carried out in the presence a palladiumcatalyst such as PdCl₂dppf (PdCl₂-1,1′-bis(diphenylphosphino)ferrocene)and a base such as potassium acetate in a solvent such as dioxane atabout 80 to 100° C. The stoichiometry of this method requires at leastone molar equivalent of the boronic acid or ester to obtain completeconversion of the compound of Formula 27 to the corresponding compoundof Formula 26. However, to obtain rapid reaction rates and high yields,an excess of the boronic acid is typically used, often at least 1.5 to2.0 molar equivalents relative to the compound of Formula 27. A widevariety of boronic acids, esters, and their derivatives can be used inthe method of Scheme 17. Particularly useful derivatives include, forexample, trialkoxy boranes such as trimethoxyborane. Coupling reactionswith boronic acids or derivatives in the presence of palladium catalystsare known, and the wide variety of known general procedures can bereadily adapted by one skilled in the art for use in the method ofScheme 17. For articles about this type of functional grouptransformation, see, for example, Tetrahedron 2000, 56, 9655-9662 andChemical Communications 2004, 1, 38.

Analogous to the method of Scheme 17, compounds of Formula 27 can becontacted with bis(pinacolato)diboron (i.e. Formula 29) to providecompounds of Formula 30. Compounds of Formula 30 can also be used in themethod of Scheme 16 to provide hydroxyphenyl derivatives of Formula 24.For a reference describing the general method of Scheme 18 seeBioorganic & Medicinal Chemistry 2011, 19, 2997-3004.

One skilled in the art recognizes that the construction of R^(3b)attached to Q¹ in the methods of Schemes 15-18 can alternatively beperformed for the construction of R^(3b) attached to Q². Therefore themethods described in Schemes 15-18 should be considered broadly usefulfor the construction of R^(3b) attached to Q¹ and for the constructionof R^(3b) attached Q². Furthermore, the methods of Schemes 15-18 canalso be performed when Q¹ or Q² is other then phenyl.

One skilled in the art will also recognize that the methods of Schemes15-18 can alternatively be carried out at other stages in thepreparation of pyrazoles of Formula 1. For example, as shown in Scheme19, using a method analogous to Scheme 15 compounds of Formula 31 can beprepared (present Example 2, Step C and Example 3, Step A illustrate thepreparation of a compound of Formula 31 using the method Scheme 15), andthen subsequently reduced using the method described in Scheme 2 oralkylated using the method described in Scheme 3 to provide compounds ofFormula 1j wherein X is CH(OH) or C(OH)R^(5a) and R^(5a) is other thenH, respectively.

Numerous other methods known to those skilled in the art can be employedfor the construction of an R^(3b) group attached to Q¹ or Q². Forexample, as depicted in Scheme 20, compounds of Formula 1k (i.e. Formula1 wherein Q¹ is phenyl, R^(3b) is W and W is a heterocycle linkedthrough nitrogen) can be prepared from compounds of Formula 32 whereinL³ is Cl, Br, I or a triflate group with heterocycles of Formula 33using Buchwald-Hartwig coupling reaction conditions. Typically thesereactions are conducted in an inert solvent in the presence of asuitable ligand, a copper (I) salt (e.g., CuI or CuBr) and a base (e.g.,sodium or potassium carbonate) at about ambient temperature to 230° C.for about 1 to 48 h. Typical ligands include 1,2-diaminocyclohexane andphenanthroline. Suitable solvents include dioxane, 1,2-diethoxyethaneand toluene. Conditions for Buchwald-Hartwig couplings are welldocumented in the literature, see for example, Tetrahedron Letters,2010, 52(38), 5052 and Journal of Medicinal Chemistry 2010, 53(10),31-8.

Alternatively, as shown in Scheme 21 (Method A), compounds of Formula 1k(i.e. Formula 1 wherein Q¹ is phenyl, R^(3b) is W and W is a heterocyclelinked through nitrogen) can be prepared from boronic acids or esters ofFormula 26 and compounds of Formula 33 using Chan-Lam couplingconditions. Typically the reaction is run in presence of a Cu(II) salt,oxygen, and a base at about ambient temperature to 150° C. for about 24to 72 h. Suitable Cu(II) salts include are Cu(OAc)₂, CuBr₂ and CuI₂,suitable bases include pyridine, quinoline and triethylamine, andsuitable solvents include dichloromethane, chloroform, diethyl ether andtetrahydrofuran. For representative conditions see Tetrahedron Letters,1998, 38, 2941 and PCT Patent Publication WO 2003/072547.

As depicted in Scheme 21 (Method B), preparation of compounds of Formula1m (i.e. Formula 1 wherein Q¹ is phenyl, R^(3b) is W, and W is aheterocycle linked through carbon) can be accomplished via thewell-known Suzuki reaction involving Pd-catalyzed cross-coupling of anheterocyclic iodide or bromide of Formula 34 with a boronic acid ofFormula 26. Many palladium catalysts are useful for this type oftransformation; a typical catalyst istetrakis(triphenylphosphine)palladium(0). Solvents such astetrahydrofuran, acetonitrile, diethyl ether and dioxane are suitable.For a thorough review of palladium chemistry see Li, J. J.; Gribble, G.W.; Editors; Palladium in Heterocyclic Chemistry: A Guide for theSynthetic Chemist, Elsevier: Oxford, U K, 2000. For representativejournal references, see, for example, Angewandte Chemie InternationalEdition, 2006, 45, 3484 and Tetrahedron Letters, 2002, 58(14), 2885.

Cyclic boronates of Formula 30 are also useful in the method of Scheme21.

One skilled in the art recognizes that the construction of R^(3b)attached to Q¹ in the methods of Schemes 20 and 21 can alternatively beperformed for the construction of R^(3b) attached to Q². Therefore themethods described in Schemes 20 and 21 should be considered broadlyuseful for construction of R^(3b) attached to either Q¹ or Q².

Furthermore, a wide variety of alternative methods exist for theconstruction of other R^(3b) groups, including well documentedfunctional group transformations of ketones, esters, acids, aldehydes,nitriles and the like. For example, as depicted in Scheme 22, reactionof an aldehyde or ketone of Formula 35 with a hydrazine of Formula 36provides compounds of Formula 1n (i.e. Formula 1 wherein Q¹ is phenyland R^(3a) is —CR^(10c)═NNR^(9a)R^(9b)). For leading references teachingthis method see Tetrahedron 2000, 56(41), 8071-8076, Journal of OrganicChemistry 2005, 70(2), 596-602 and Synthetic Communications 1997, 27(7),1199-1207.

Aldehydes and ketones of Formula 35 can be prepared from thecorresponding bromo, iodo or triflate derivatives via transitionmetal-catalyzed cross-coupling reactions. For conditions see J. Am.Chem. Soc., 2008, 130, 15549-15563, Journal of Medicinal Chemistry 2003,46, 5651-5662 and Tetrahedron 2003, 59, 8199-8202.

Additionally, it will be recognized by one skilled in the art thatvarious functional groups can be converted into others to providedifferent compounds of Formula 1. For example, compounds of Formula 1 inwhich R² is methyl, ethyl or cyclopropyl can be modified by free-radicalhalogenation to form compounds of Formula 1 wherein R² is halomethyl orhalocyclopropyl. The halomethyl compounds can themselves be used asintermediates to prepare compounds of Formula 1 wherein R² ishydroxymethyl or cyanomethyl. Compounds of Formula 1 or intermediatesfor their preparation may contain aromatic nitro groups, which can bereduced to amino groups, and then be converted via reactions well-knownin the art, such as the Sandmeyer reaction, to various halides,providing other compounds of Formula 1. By similarly known reactions,aromatic amines (anilines) can be converted via diazonium salts tophenols, which can then be alkylated to prepare compounds of Formula 1with alkoxy substituents. Likewise, aromatic halides such as bromides oriodides, prepared via the Sandmeyer reaction, can be reacted withalcohols under copper-catalyzed conditions, such as the Ullmann reactionor known modifications thereof, to provide compounds of Formula 1 thatcontain alkoxy substituents. Additionally, some halogen groups, such asfluorine or chlorine, can be displaced with alcohols under basicconditions to provide compounds of Formula 1 containing thecorresponding alkoxy substituents. Compounds of Formula 1, or precursorsthereof, in which R² is halide, preferably bromide or iodide, areparticularly useful intermediates for transition metal-catalyzedcross-coupling reactions to prepare compounds of Formula 1. These typesof reactions are well documented in the literature; see, for example,Tsuji in Transition Metal Reagents and Catalysts: Innovations in OrganicSynthesis, John Wiley and Sons, Chichester, 2002; Tsuji in Palladium inOrganic Synthesis, Springer, 2005; and Miyaura and Buchwald in CrossCoupling Reactions: A Practical Guide, 2002; and references citedtherein.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula 1 may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula 1. One skilled in the artwill also recognize that it may be necessary to perform a combination ofthe steps illustrated in the above schemes in an order other than thatimplied by the particular sequence presented to prepare the compounds ofFormula 1.

The above reactions can also in many cases be performed in alternatesequence, such as the preparation of 1H pyrazoles for use in thereaction in Scheme 7 by reactions illustrated later for the generalpreparation of substituted pyrazoles. The presence of certain functionalgroups may not be compatible with all of these reaction conditions, andthe use of protecting groups may be desirable for obtaining the desiredproducts with improved yields and or purity.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Steps in the following Examples illustrate a procedure foreach step in an overall synthetic transformation, and the startingmaterial for each step may not have necessarily been prepared by aparticular preparative run whose procedure is described in otherExamples or Steps. Percentages are by weight except for chromatographicsolvent mixtures or where otherwise indicated. Parts and percentages forchromatographic solvent mixtures are by volume unless otherwiseindicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane in CDCl₃ unless otherwise noted; “s” means singlet,“d” means doublet, “t” means triplet, “m” means multiplet, “dd” meansdoublet of doublets and “dt” means doublet of triplets.

Example 1 Preparation ofα-(2-chloro-4-fluorophenyl)-5-[2,6-difluoro-4-(1H-pyrazol-1-yl)phenyl]-1,3-dimethyl-1H-pyrazole-4-methanol(Compound 3) Step A: Preparation of 4-bromo-2,6-difluorobenzoyl chloride

A mixture of 4-bromo-2,6-difluorobenzoic acid (2.0 g, 9.1 mmol) andthionyl chloride (10 mL) was heated at 100° C. for 16 h. The reactionmixture was distilled under reduced pressure, diluted with toluene (10mL), and again distilled under reduced pressure to provide the titlecompound.

Step B: Preparation of(2Z)-1-(4-bromo-2,6-difluorophenyl)-3-hydroxy-2-buten-1-one

To a mixture of 2,4-pentanedione (0.93 mL, 9.1 mmol) in acetonitrile (10mL) was added magnesium chloride (0.95 g, 10 mmol). After 0.5 h, thereaction mixture was cooled to 0° C. and then triethylamine (2.0 g, 19mmol) was added, followed by 4-bromo-2,6-difluorobenzoyl chloride (i.e.the product of Step A) (2.3 g, 9.0 mmol) in acetonitrile (10 mL). Afteran additional 2 h, the reaction mixture was concentrated under reducedpressure, hydrochloric acid (concentrated, 2 mL) was added and themixture was heated at 100° C. for 2 h. The reaction mixture was cooledto room temperature, water (100 mL) was added and the resulting mixturewas extracted with ethyl acetate (3×5 mL). The combined organic layerswere washed with saturated aqueous sodium chloride solution (50 mL),dried over sodium sulfate, filtered and concentrated under reducedpressure. The resulting material was purified by column chromatographyon silica gel eluting with 5% ethyl acetate in petroleum ether toprovide the title compound as a yellow oil (1.65 g).

1H NMR (CDCl₃): δ 15.39 (s, 1H), 7.16 (d, 2H), 5.84 (s, 1H), 2.17 (s,3H).

Step C: Preparation of5-(4-bromo-2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole

To a mixture triethylamine (1.2 g, 12.0 mmol) and methylhydrazine (0.42mL, 7.942 mmol) at 0° C. was added a solution of(2Z)-1-(4-bromo-2,6-difluorophenyl)-3-hydroxy-2-buten-1-one (i.e. theproduct of Step B) (1.1 g, 4.0 mmol) in ethanol (20 mL). The reactionmixture was stirred at room temperature for 18 h and then concentratedunder reduced pressure. Water (70 mL) was added to the resultingmaterial and the mixture was extracted with ethyl acetate (2×50 mL),dried over sodium sulfate and concentrated under reduced pressure. Theresidue was purified by column chromatography on silica gel eluting with4% ethyl acetate in petroleum ether to provide the title compound as anoff-white solid (420 mg).

1H NMR (CDCl₃): δ 7.24-7.19 (m, 2H), 6.15 (s, 1H), 3.69 (s, 3H), 2.31(s, 3H).

Step D: Preparation of[5-(4-bromo-2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl](2-chloro-4-fluorophenyl)methanone

To a mixture of 5-(4-bromo-2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazole(i.e. the product of Step C) (0.6 g, 2.1 mmol) in tetrachloroethane (8mL) at 0° C. was added aluminum chloride (0.70 g, 5.2 mmol), followed2-chloro-4-fluorobenzoyl chloride (1.4 g, 7.3 mmol). The reactionmixture was heated at 150° C. for 12 h. After cooling to roomtemperature, the reaction mixture was quenched with ice water and thenextracted with ethyl acetate (4×100 mL). The combined organic layerswere dried over sodium sulfate and concentrated under reduced pressure.The resulting material was purified by column chromatography on silicagel eluting with 10% ethyl acetate in petroleum ether to provide thetitle compound as an off-white solid (0.5 g).

1H NMR (DMSO-d₆): δ 7.47 (d, 2H), 7.32-7.27 (m, 2H), 7.10 (dt, 1H), 3.61(s, 3H), 2.31 (s, 3H).

Step E: Preparation of(2-chloro-4-fluorophenyl)[5-[2,6-difluoro-4-(1H-pyrazol-1-yl)phenyl]-1,3-dimethyl-1H-pyrazol-4-yl]methanone

To a solution of[5-(4-bromo-2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl](2-chloro-4-fluorophenyl)methanone(i.e. the product of Step D) (0.30 g, 0.70 mmol) in 1,4-dioxane (4.5 mL)was added 1H-pyrazole (51 mg, 0.745 mmol), potassium carbonate (374 mg,2.709 mmol) and copper iodide (26 mg, 0.14 mmol). The reaction mixturewas sparged with argon gas for 20 minutes and thentrans-N,N-dimethyl-1,2-cyclohexanediamine (0.02 mL, 0.14 mmol) was addedand the mixture was heated at 110° C. for 24 h. After cooling to roomtemperature, the reaction mixture was filtered through a pad of Celite®(diatomaceous filter aid) on a sintered glass frit funnel. The filtratewas added to water (50 mL) and then extracted with ethyl acetate (2×50mL). The combined organic layers were dried over sodium sulfate,filtered and concentrated under reduced pressure. The resulting materialwas purified by column chromatography on silica gel eluting with 20%ethyl acetate in petroleum ether to provide the title compound as anoff-white solid (280 mg).

¹H NMR (DMSO-d₆): δ 8.60 (d, 1H), 7.84 (d, 1H), 7.61 (d, 2H), 7.35-7.32(m, 1H), 7.28-7.24 (m, 1H), 7.12-7.07 (m, 1H), 6.63 (t, 1H), 3.65 (s,3H), 2.33 (s, 3H).

Step F: Preparation ofα-(2-chloro-4-fluorophenyl)-5-[2,6-difluoro-4-(1H-pyrazol-1-yl)phenyl]-1,3-dimethyl-1H-pyrazole-4-methanol

To a mixture of(2-chloro-4-fluorophenyl)[5-[2,6-difluoro-4-(1H-pyrazol-1-yl)phenyl]-1,3-dimethyl-1H-pyrazol-4-yl]methanone(i.e. the product of Step E) (280 mg, 0.67 mmol) in ethanol (10 mL) at0° C. was added sodium borohydride (250 mg, 6.7 mmol). After 18 h, thereaction mixture was quenched with ice water and extracted with ethylacetate (3×30 mL). The combined organic layers were dried over sodiumsulfate, filtered and concentrated under reduced pressure. The resultingmaterial was purified by column chromatography on silica gel elutingwith 25% ethyl acetate in petroleum ether to provide the title compound,a compound of the present invention, as a white solid (190 mg).

¹H NMR (DMSO-d₆): δ 8.63 (d, 1H), 7.84 (d, 1H), 7.69 (d, 1H), 7.56 (d,1H), 7.47-7.43 (m, 1H), 7.18 (dd, 1H), 6.93-6.88 (m, 1H), 6.63 (t, 1H),5.71 (s, 2H), 3.47 (s, 3H), 2.18 (s, 3H).

Example 2 Preparation ofα-(2-chloro-4-fluorophenyl)-5-[4-(cyclopropylmethoxy)-2,6-difluorophenyl]-1,3-dimethyl-1H-pyrazole-4-methanol(Compound 10) Step A: Preparation of(2-chloro-4-fluorophenyl)[5-[2,6-difluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3-dimethyl-1H-pyrazol-4-yl]methanone

A solution of[5-(4-bromo-2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-4-yl](2-chloro-4-fluorophenyl)methanone(i.e. the product of Example 1, Step D) (4.8 g, 11 mmol) andbis(pinacolato)diborane (5.5 g, 22 mmol) in dioxane (40 mL) was spargedwith a stream of argon gas for 10 minutes, and then[1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II) (0.88 g,1.1 mmol) and potassium acetate (3.1 g, 33 mmol) were added to thereaction mixture. The reaction mixture was heated at 80° C. for 18 h,cooled to room temperature, and then filtered through a pad of Celite®(diatomaceous filter aid) on a sintered glass frit funnel. The filtrateconcentrated under reduced pressure and the resulting material wasdiluted with water and extracted with ethyl acetate (3×100 mL). Thecombined organic layers were washed with water and saturated sodiumchloride solution, and then dried over sodium sulfate, filtered andconcentrated under reduced pressure to provide the title compound as abrown oil (6 g).

Step B: Preparation of(2-chloro-4-fluorophenyl)[5-(2,6-difluoro-4-hydroxyphenyl)-1,3-dimethyl-1H-pyrazol-4-yl]methanone

To a mixture of(2-chloro-4-fluorophenyl)[5-[2,6-difluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1,3-dimethyl-1H-pyrazol-4-yl]methanone(i.e. the product of Step A) (0.25 g, 0.51 mmol) in dichloromethane (7ml) was added N,N,4-trimethylbenzenamine N-oxide (prepared according toOrganic Letters 2012, 14, 3494-3497) (0.092 g, 0.61 mmol). After 3 h,the reaction mixture was diluted with water and extracted withdichloromethane. The combined organic layers were dried over sodiumsulfate, filtered and concentrated under reduced pressure. The resultingmaterial was purified by column chromatography on silica gel elutingwith 30% ethyl acetate in petroleum ether to provide the title compoundas an off-white solid (0.060 g).

¹H NMR (DMSO-d₆): δ 10.73 (s, 1H), 7.28-7.18 (m, 2H), 7.10-7.08 (m, 1H),6.35 (d, 2H), 3.57 (s, 3H), 2.35 (s, 3H).

Step C: Preparation of(2-chloro-4-fluorophenyl)[5-[4-(cyclopropylmethoxy)-2,6-difluorophenyl]-1,3-dimethyl-1H-pyrazol-4-yl]methanone

To a mixture of(2-chloro-4-fluorophenyl)[5-(2,6-difluoro-4-hydroxyphenyl)-1,3-dimethyl-1H-pyrazol-4-yl]methanone(i.e. the product of Step B) (0.090 g, 0.24 mmol) and potassiumcarbonate (0.065 g, 0.44 mmol) in N,N-dimethylformamide (2 ml) was added(iodomethyl)cyclopropane (0.051 g, 0.28 mmol). After 5 h, the reactionmixture was diluted with water and extracted with ethyl acetate (2×50mL). The combined organic layers were dried over sodium sulfate,filtered and concentrated under reduced pressure. The resulting materialwas purified by column chromatography on silica gel eluting with 30%ethyl acetate in petroleum ether to provide the title compound as anoff-white solid (0.087 g).

¹H NMR (DMSO-d₆): δ 7.28-7.23 (m, 2H), 7.07 (dt, 1H), 6.66 (d, 2H), 3.82(d, 2H), 3.58 (s, 3H), 2.34 (s, 3H), 1.21-1.17 (m, 1H), 0.62-0.56 (m,2H), 0.33-0.28 (m, 2H).

Step D: Preparation ofo-(2-chloro-4-fluorophenyl)-5-[4-(cyclopropylmethoxy)-2,6-difluorophenyl]-1,3-dimethyl-1H-pyrazole-4-methanol

To a mixture of(2-chloro-4-fluorophenyl)[5-[4-(cyclopropylmethoxy)-2,6-difluorophenyl]-1,3-dimethyl-1H-pyrazol-4-yl]methanone(i.e. the product of Step C) (0.20 g, 0.46 mmol) in methanol (3 ml) wasadded sodium borohydride (0.052 g, 1.4 mmol). After stirring for 5 h,the reaction was quenched with ice water and then the methanol wasremoved under reduced pressure. The resulting mixture was extracted withethyl acetate (2×25 mL) and the combined organic layers were dried oversodium sulfate, filtered and concentrated under reduced pressure. Theresulting material was purified by preparative TLC (GF 254, preparativesilica gel plate) eluting with 20% ethyl acetate in petroleum ether toprovide the title compound, a product of the present invention, as anoff-white solid (0.10 g).

¹H NMR (DMSO-d₆): δ 7.45-7.40 (m, 1H), 7.16 (dd, 1H), 6.94 (dt, 1H),6.75 (d, 1H), 6.61 (d, 1H), 5.66-5.62 (m, 2H), 3.86 (d, 2H), 3.42 (s,3H), 2.15 (s, 3H), 1.26-1.21 (m, 1H), 0.63-0.57 (m, 2H), 0.36-0.31 (m,2H).

Example 3 Preparation ofα-(2-chloro-4-fluorophenyl)-5-[2,6-difluoro-4-(3-methylbutoxy)phenyl]-1,3-dimethyl-1H-pyrazole-4-methanol(Compound 9) Step A: Preparation of(2-chloro-4-fluorophenyl)[5-[2,6-difluoro-4-(3-methylbutoxy)phenyl]-1,3-dimethyl-1H-pyrazol-4-yl]methanone

To a mixture of(2-chloro-4-fluorophenyl)[5-(2,6-difluoro-4-hydroxyphenyl)-1,3-dimethyl-1H-pyrazol-4-yl]methanone(i.e. the product of Example 2, Step B) (0.066 g, 0.17 mmol) andpotassium carbonate (0.047 g, 0.35 mmol) in N,N-dimethylformamide (2 ml)was added 1-iodo-3-methylbutane (0.030 ml, 0.21 mmol). After 5 h, thereaction mixture was diluted with water and extracted with ethyl acetate(2×50 mL). The combined organic layers were dried over sodium sulfate,filtered and concentrated under reduced pressure. The resulting materialwas purified by column chromatography on silica gel eluting with 30%ethyl acetate in petroleum ether to provide the title compound as anoff-white solid (50 mg).

¹H NMR (CDCl₃): δ 7.23-7.19 (m, 1H), 6.87 (dd, 1H), 6.82-6.77 (m, 1H),6.30 (d, 2H), 3.91 (t, 2H), 3.65 (s, 3H), 2.46 (s, 3H), 1.82-1.77 (m,1H), 1.68-1.63 (m, 2H), 0.97 (d, 6H).

Step B: Preparation ofα-(2-chloro-4-fluorophenyl)-5-[2,6-difluoro-4-(3-methylbutoxy)phenyl]-1,3-dimethyl-1H-pyrazole-4-methanol

To mixture of(2-chloro-4-fluorophenyl)[5-[2,6-difluoro-4-(3-methylbutoxy)phenyl]-1,3-dimethyl-1H-pyrazol-4-yl]methanone(i.e. the product of Step A) (0.05 g, 0.111 mmol) in methanol (2 ml) wasadded sodium borohydride (0.0080 g, 0.22 mmol). After 5 h, the reactionmixture was quenched with ice water and then the methanol was removedunder reduced pressure. The resulting mixture was extracted with ethylacetate (2×25 mL) and the combined organic layers were dried over sodiumsulfate, filtered and concentrated under reduced pressure. The resultingmaterial was purified by preparative TLC (GF 254, preparative silica gelplate) eluting with 20% ethyl acetate in petroleum ether to provide thetitle compound, a product of the present invention, as an off-whitesolid (30 mg).

¹H NMR (DMSO-d6): δ 7.44-7.41 (m, 1H), 7.15 (d, 1H), 6.91 (t, 1H), 6.75(d, 1H), 6.60 (d, 1H), 5.67 (d, 1H), 5.61 (d, 1H), 4.06-4.00 (m, 2H),3.41 (s, 3H), 2.16 (s, 3H), 1.81-1.74 (m, 1H), 1.64-1.59 (m, 2H), 0.94(d, 6H).

By the procedures described herein together with methods known in theart, the compounds disclosed in the Tables that follow can be prepared.The following abbreviations are used in the Tables which follow: i meansiso, c means cyclo, n means normal, s means secondary, Me means methyl,Bu means butyl, Pr means propyl, MeO means methoxy, CN means cyano, andPh means phenyl.

TABLE 1

Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2,6-di-F. R^(3b) R^(3b) R^(3b)R^(3b) 4-(HC≡CCH₂O)— 4-(MeC≡CCH₂O)— 4-(HC≡CCH₂CH₂O)— 4-(MeC≡CCH₂CH₂O)—4-(H₂C═CHCH₂O)— 4-(MeHC═CCH₂O)— 4-(ClHC═CHCH₂O)— 4-(Cl₂C═CHCH₂O)—4-(HC≡C(Me)CHO)— 4-(H₂C═C(Me)CHO)— 4-(H₂C═CHCH(Me)O)—4-(MeHC═CHCH(Me)O)— 4-n-butoxy 4-i-butoxy 4-s-butoxy 4-n-pentoxy4-i-pentoxy 4-s-pentoxy 4-(c-Pr—HC═CHCH₂O)- 4-(c-Pr—C≡CCH₂O)—4-(c-Pr—HC═CH)— 4-(c-Pr—C≡C)— 4-(c-Pr—CH₂O)— 4-(c-Bu—CH₂O)—4-(c-pentyl—CH₂O)— 4-(HO—N═CH)— 4-(MeO—N═CH)— 4-(HO—N═C(Me))—4-(MeO—N═C(Me))— 4-(MeHC═N—O)— 4-(Me₂C═N—O)— 4-(H₂C═N—O)— 4-(H₂N—N═CH)—4-(MeNH—N═CH)— 4-(Me₂N—N═CH)— 4-(H₂N—N═C(Me))— 4-(MeNH—N═C(Me))—4-(Me₂N—N═C(Me))— 4-(MeHC═N—NH)— 4-(Me₂C═N—NH)— 4-(H₂C═N—NH)—4-(MeHC═N—N(Me))— 4-(Me₂C═N—N(Me))— 4-(H₂C═N—N(Me))— 3-(HC≡CCH₂O)—3-(MeC≡CCH₂O)— 3-(HC≡CCH₂CH₂O)— 3-(MeC≡CCH₂CH₂O)— 3-(H₂C═CHCH₂O)—3-(MeHC═CHCH₂O)— 3-(ClHC═CHCH₂O)— 3-(Cl₂C═CHCH₂O)— 3-(HC≡C(Me)CHO)—3-(H₂C═C(Me)CHO)— 3-(H₂C═CHCH(Me)O)— 3-(MeHC═CHCH(Me)O)— 3-n-butoxy3-i-butoxy 3-s-butoxy 3-n-pentoxy 3-i-pentoxy 3-s-pentoxy3-(c-Pr—HC═CHCH₂O)— 3-(c-Pr—C≡CCH₂O)— 3-(c-Pr—HC═CH)— 3-(c-Pr—C≡C)—3-(c-Pr—CH₂O)— 3-(c-Bu—CH₂O)— 3-(c-pentyl—CH₂O)— 3-(HO—N═CH)—3-(MeO—N═CH)— 3-(HO—N═C(Me))— 3-(MeO—N═C(Me))— 3-(MeHC═N—O)—3-(Me₂C═N—O)— 3-(H₂C═N—O)— 3-(H₂N—N═CH)— 3-(MeNH—N═CH)— 3-(Me₂N—N═CH)—3-(H₂N—N═C(Me))— 3-(MeNH—N═C(Me))— 3-(Me₂N—N═C(Me))— 3-(MeHC═N—NH)—3-(Me₂C═N—NH)— 3-(H₂C═N—NH)— 3-(MeHC═N—N(Me))— 3-(Me₂C═N—N(Me))—3-(H₂C═N—N(Me))— 3-CF₃-1H-pyrazol-1-yl 3-Me-1H-pyrazol-1-yl3-F-1H-pyrazol-1-yl 3-Br-1H-pyrazol-1-yl 4-CF₃-1H-pyrazol-1-yl4-Me-1H-pyrazol-1-yl 4-F-1H-pyrazol-1-yl 4-Br-1H-pyrazol-1-yl5-CF₃-1H-pyrazol-1-yl 5-Me-1H-pyrazol-1-yl 5-F-1H-pyrazol-1-yl5-Br-1H-pyrazol-1-yl 3-CHF₂-1H-pyrazol-1-yl 3-Et-1H-pyrazol-1-yl3-C1-1H-pyrazol-1-yl 3-I-1H-pyrazol-1-yl 4-CHF₂-1H-pyrazol-1-yl3-Et-1H-pyrazol-1-yl 4-C1-1H-pyrazol-1-yl 4-I-1H-pyrazol-1-yl5-CHF₂-1H-pyrazol-1-yl 3-Et-1H-pyrazol-1-yl 5-C1-1H-pyrazol-1-yl5-I-pyrazol-1-yl 1H-pyrazol-1-yl 1H-1,2,3-triazol-1-yl1H-1,2,3-triazol-1-yl 1H-1,2,3-triazol-2-yl 1H-pyrrol-1-yl1-Me-1H-pyrazol-3-yl 1-CF₃-1H-pyrazol-3-yl

The present disclosure also includes Tables 1A through 215A, each ofwhich is constructed the same as Table 1 above, except that the rowheading in Table 1 (i.e. “Q² is 2,4,6-tri-F-Ph, (R^(3a))_(p) is2,6-di-F”) is replaced with the respective row headings shown below. ForExample, in Table 1A the row heading is “Q² is 2,4,6-tri-F-Ph,(R^(3a))_(p) is 2-F”, and R^(3b) is as defined in Table 1 above. Thus,the first entry in Table 1A specifically discloses5-[2-fluoro-4-(-propyn-1-yloxy)phenyl]-1,3-dimethyl-N-(2,4,6-trifluorophenyl)-1H-pyrazol-4-amine.Tables 2A through 215A are constructed similarly.

Table Row Heading  1A Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-F.  2A Q²is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-Cl.  3A Q² is 2,4,6-tri-F—Ph,(R^(3a))_(p) is 2-Br.  4A Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-Me. 5A Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  6A Q² is2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  7A Q² is 2,4,6-tri-F—Ph,(R^(3a))_(p) is 2,6-di-Cl.  8A Q² is 2,6-di-F—Ph, (R^(3a))_(p) is2,6-di-F.  9A Q² is 2,6-di-F—Ph, (R^(3a))_(p) is 2-F.  10A Q² is2,6-di-F—Ph, (R^(3a))_(p) is 2-Cl.  11A Q² is 2,6-di-F—Ph, (R^(3a))_(p)is 2-Br.  12A Q² is 2,6-di-F—Ph, (R^(3a))_(p) is 2-Me.  13A Q² is2,6-di-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  14A Q² is 2,6-di-F—Ph,(R^(3a))_(p) is 2-Cl, 6-F.  15A Q² is 2,6-di-F—Ph, (R^(3a))_(p) is2,6-di-Cl.  16A Q² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2,6-di-F.  17AQ² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-F.  18A Q² is2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-Cl.  19A Q² is 2,6-di-F-4-MeO—Ph,(R^(3a))_(p) is 2-Br.  20A Q² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is2-Me.  21A Q² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  22A Q²is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  23A Q² is2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2,6-di-Cl.  24A Q² is2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2,6-di-F.  25A Q² is 2,6-di-F-4-Me—Ph,(R^(3a))_(p) is 2-F.  26A Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2-Cl. 27A Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2-Br.  28A Q² is2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2-Me.  29A Q² is 2,6-di-F-4-Me—Ph,(R^(3a))_(p) is 2-F, 6-Cl  30A Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is2-Cl, 6-F.  31A Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2,6-di-Cl.  32AQ² is 2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2,6-di-F.  33A Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-F.  34A Q² is 2,6-di-F-4-CN—Ph,(R^(3a))_(p) is 2-Cl.  35A Q² is 2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-Br. 36A Q² is 2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-Me.  37A Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  38A Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  39A Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2,6-di-Cl.  40A Q² is2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2,6-di-F.  41A Q² is 2,6-di-F-4-Cl—Ph,(R^(3a))_(p) is 2-F.  42A Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2-Cl. 43A Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2-Br.  44A Q² is2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2-Me.  45A Q² is 2,6-di-F-4-Cl—Ph,(R^(3a))_(p) is 2-F, 6-Cl.  46A Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is2-Cl, 6-F.  47A Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2,6-di-Cl.  48AQ² is 2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2,6-di-F.  49A Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-F.  50A Q² is 2,6-di-F-4-Br—Ph,(R^(3a))_(p) is 2-Cl.  51A Q² is 2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-Br. 52A Q² is 2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-Me.  53A Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  54A Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  55A Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2,6-di-Cl.  56A Q² is 2,4-di-F—Ph,(R^(3a))_(p) is 2,6-di-F.  57A Q² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-F. 58A Q² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-Cl.  59A Q² is 2,4-di-F—Ph,(R^(3a))_(p) is 2-Br.  60A Q² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-Me  61AQ² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  62A Q² is 2,4-di-F—Ph,(R^(3a))_(p) is 2-Cl, 6-F.  63A Q² is 2,4-di-F—Ph, (R^(3a))_(p) is2,6-di-Cl  64A Q² is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2,6-di-F.  65A Q²is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-F.  66A Q² is 2,4-di-F-6-Cl—Ph,(R^(3a))_(p) is 2-Cl.  67A Q² is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-Br. 68A Q² is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-Me.  69A Q² is2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  70A Q² is2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  71A Q² is2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2,6-di-Cl.  72A Q² is2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2,6-di-F  73A Q² is 2,4-di-F-6-Br—Ph,(R^(3a))_(p) is 2-F.  74A Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2-Cl. 75A Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2-Br.  76A Q² is2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2-Me.  77A Q² is 2,4-di-F-6-Br—Ph,(R^(3a))_(p) is 2-F, 6-Cl.  78A Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is2-Cl, 6-F.  79A Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2,6-di-Cl.  80AQ² is 2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-F.  81A Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-F.  82A Q² is 2-Cl-4-Me-6-F—Ph,(R^(3a))_(p) is 2-Cl.  83A Q² is 2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Br. 84A Q² is 2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Me.  85A Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  86A Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  87A Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl.  88A Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-F.  89A Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F.  90A Q² is 2-Cl-4-MeO-6-F—Ph,(R^(3a))_(p) is 2-Cl.  91A Q² is 2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is2-Br.  92A Q² is 2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Me.  93A Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  94A Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  95A Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl.  96A Q² is2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-F.  97A Q² is 2-Br-4-Me-6-F—Ph,(R^(3a))_(p) is 2-F.  98A Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Cl. 99A Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Br. 100A Q² is2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Me 101A Q² is 2-Br-4-Me-6-F—Ph,(R^(3a))_(p) is 2-F, 6-Cl. 102A Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is2-Cl, 6-F. 103A Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl. 104AQ² is 2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-F. 105A Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F. 106A Q² is 2-Br-4-MeO-6-F—Ph,(R^(3a))_(p) is 2-Cl. 107A Q² is 2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is2-Br. 108A Q² is 2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Me. 109A Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl. 110A Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F. 111A Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl. 112A Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2,6-di-F. 113A Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-F. 114A Q² is 2,6-di-Cl-4-Me—Ph,(R^(3a))_(p) is 2-Cl. 115A Q² is 2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is2-Br. 116A Q² is 2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-Me. 117A Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-F, 6-Cl 118A Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-Cl, 6-F. 119A Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2,6-di-Cl. 120A Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2,6-di-F. 121A Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-F. 122A Q² is 2,6-di-Br-4-Me—Ph,(R^(3a))_(p) is 2-Cl. 123A Q² is 2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is2-Br. 124A Q² is 2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-Me. 125A Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-F, 6-Cl. 126A Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-Cl, 6-F. 127A Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2,6-di-Cl. 128A Q² is2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2,6-di-F. 129A Q² is 2,4,6-tri-Cl—Ph,(R^(3a))_(p) is 2-F. 130A Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2-Cl.131A Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2-Br. 132A Q² is2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2-Me. 133A Q² is 2,4,6-tri-Cl—Ph,(R^(3a))_(p) is 2-F, 6-Cl. 134A Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is2-Cl, 6-F. 135A Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2,6-di-Cl. 136AQ² is 2-Cl-4-F, (R^(3a))_(p) is 2,6-di-F. 137A Q² is 2-Cl-4-F,(R^(3a))_(p) is 2-F. 138A Q² is 2-Cl-4-F, (R^(3a))_(p) is 2-Cl. 139A Q²is 2-Cl-4-F, (R^(3a))_(p) is 2-Br. 140A Q² is 2-Cl-4-F, (R^(3a))_(p) is2-Me. 141A Q² is 2-Cl-4-F, (R^(3a))_(p) is 2-F, 6-Cl 142A Q² is2-Cl-4-F, (R^(3a))_(p) is 2-Cl, 6-F 143A Q² is 2-Cl-4-F, (R^(3a))_(p) is2,6-di-Cl. 144A Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2,6-di-F. 145A Q² is2-Cl-4-Me, (R^(3a))_(p) is 2-F. 146A Q² is 2-Cl-4-Me, (R^(3a))_(p) is2-Cl. 147A Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2-Br. 148A Q² is 2-Cl-4-Me,(R^(3a))_(p) is 2-Me. 149A Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2-F, 6-Cl.150A Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2-Cl, 6-F. 151A Q² is 2-Cl-4-Me,(R^(3a))_(p) is 2,6-di-Cl. 152A Q² is 2-Cl-4-MeO, (R^(3a))_(p) is2,6-di-F. 153A Q² is 2-Cl-4-MeO, (R^(3a))_(p) is 2-F 154A Q² is2-Cl-4-MeO, (R^(3a))_(p) is 2-Cl. 155A Q² is 2-Cl-4-MeO, (R^(3a))_(p) is2-Br. 156A Q² is 2-Cl-4-MeO, (R^(3a))_(p) is 2-Me . . . 157A Q² is2-Cl-4-MeO, (R^(3a))_(p) is 2-F, 6-Cl. 158A Q² is 2-Cl-4-MeO,(R^(3a))_(p) is 2-Cl, 6-F. 159A Q² is 2-Cl-4-MeO, (R^(3a))_(p) is2,6-di-Cl. 160A Q² is 2-Br-4-F, (R^(3a))_(p) is 2,6-di-F. 161A Q² is2-Br-4-F, (R^(3a))_(p) is 2-F. 162A Q² is 2-Br-4-F, (R^(3a))_(p) is2-Cl. 163A Q² is 2-Br-4-F, (R^(3a))_(p) is 2-Br. 164A Q² is 2-Br-4-F,(R^(3a))_(p) is 2-Me. 165A Q² is 2-Br-4-F, (R^(3a))_(p) is 2-F, 6-Cl.166A Q² is 2-Br-4-F, (R^(3a))_(p) is 2-Cl, 6-F. 167A Q² is 2-Br-4-F,(R^(3a))_(p) is 2,6-di-Cl. 168A Q² is 2-Br-4-Me, (R^(3a))_(p) is2,6-di-F. 169A Q² is 2-Br-4-Me, (R^(3a))_(p) is 2-F. 170A Q² is2-Br-4-Me, (R^(3a))_(p) is 2-Cl. 171A Q² is 2-Br-4-Me, (R^(3a))_(p) is2-Br. 172A Q² is 2-Br-4-Me, (R^(3a))_(p) is 2-Me. 173A Q² is 2-Br-4-Me,(R^(3a))_(p) is 2-F, 6-Cl. 174A Q² is 2-Br-4-Me, (R^(3a))_(p) is 2-Cl,6-F. 175A Q² is 2-Br-4-Me, (R^(3a))_(p) is 2,6-di-Cl. 176A Q² is2-Br-4-MeO, (R^(3a))_(p) is 2,6-di-F. 177A Q² is 2-Br-4-MeO,(R^(3a))_(p) is 2-F. 178A Q² is 2-Br-4-MeO, (R^(3a))_(p) is 2-Cl. 179AQ² is 2-Br-4-MeO, (R^(3a))_(p) is 2-Br. 180A Q² is 2-Br-4-MeO,(R^(3a))_(p) is 2-Me. 181A Q² is 2-Br-4-MeO, (R^(3a))_(p) is 2-F, 6-Cl.182A Q² is 2-Br-4-MeO, (R^(3a))_(p) is 2-Cl, 6-F. 183A Q² is 2-Br-4-MeO,(R^(3a))_(p) is 2,6-di-Cl. 184A Q² is 2,4-di-Cl, (R^(3a))_(p) is2,6-di-F. 185A Q² is 2,4-di-Cl, (R^(3a))_(p) is 2-F. 186A Q² is2,4-di-Cl, (R^(3a))_(p) is 2-Cl. 187A Q² is 2,4-di-Cl, (R^(3a))_(p) is2-Br. 188A Q² is 2,4-di-Cl, (R^(3a))_(p) is 2-Me. 189A Q² is 2,4-di-Cl,(R^(3a))_(p) is 2-F, 6-Cl. 190A Q² is 2,4-di-Cl, (R^(3a))_(p) is 2-Cl,6-F. 191A Q² is 2,4-di-Cl, (R^(3a))_(p) is 2,6-di-Cl. 192A Q² is2,6-di-Cl, (R^(3a))_(p) is 2,6-di-F. 193A Q² is 2,6-di-Cl, (R^(3a))_(p)is 2-F. 194A Q² is 2,6-di-Cl, (R^(3a))_(p) is 2-Cl. 195A Q² is2,6-di-Cl, (R^(3a))_(p) is 2-Br. 196A Q² is 2,6-di-Cl, (R^(3a))_(p) is2-Me. 197A Q² is 2,6-di-Cl, (R^(3a))_(p) is 2-F, 6-Cl. 198A Q² is2,6-di-Cl, (R^(3a))_(p) is 2-Cl, 6-F. 199A Q² is 2,6-di-Cl, (R^(3a))_(p)is 2,6-di-Cl. 200A Q² is 2,4-di-Me, (R^(3a))_(p) is 2,6-di-F. 201A Q² is2,4-di-Me, (R^(3a))_(p) is 2-F. 202A Q² is 2,4-di-Me, (R^(3a))_(p) is2-Cl. 203A Q² is 2,4-di-Me, (R^(3a))_(p) is 2-Br. 204A Q² is 2,4-di-Me,(R^(3a))_(p) is 2-Me. 205A Q² is 2,4-di-Me, (R^(3a))_(p) is 2-F, 6-Cl.206A Q² is 2,4-di-Me, (R^(3a))_(p) is 2-Cl, 6-F. 207A Q² is 2,4-di-Me,(R^(3a))_(p) is 2,6-di-Cl. 208A Q² is 2,6-di-Me, (R^(3a))_(p) is2,6-di-F. 209A Q² is 2,6-di-Me, (R^(3a))_(p) is 2-F. 210A Q² is2,6-di-Me, (R^(3a))_(p) is 2-Cl 211A Q² is 2,6-di-Me, (R^(3a))_(p) is2-Br. 212A Q² is 2,6-di-Me, (R^(3a))_(p) is 2-Me. 213A Q² is 2,6-di-Me,(R^(3a))_(p) is 2-F, 6-Cl. 214A Q² is 2,6-di-Me, (R^(3a))_(p) is 2-Cl,6-F. 215A Q² is 2,6-di-Me, (R^(3a))_(p) is 2,6-di-Cl.

TABLE 2

Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2,6-di-F. R^(3b) R^(3b) R^(3b)R^(3b) 4-(HC≡CCH₂O)— 4-(MeC≡CCH₂O)— 4-(HC≡CCH₂CH₂O)— 4-(MeC≡CCH₂CH₂O)—4-(H₂C═CHCH₂O)— 4-(MeHC═CCH₂O)— 4-(ClHC═CHCH₂O)— 4-(Cl₂C═CHCH₂O)—4-(HC≡C(Me)CHO)— 4-(H₂C═C(Me)CHO)— 4-(H₂C═CHCH(Me)O)—4-(MeHC═CHCH(Me)O)— 4-n-butoxy 4-i-butoxy 4-s-butoxy 4-n-pentoxy4-i-pentoxy 4-s-pentoxy 4-(c-Pr—HC═CHCH₂O)— 4-(c-Pr—C≡CCH₂O)—4-(c-Pr—HC═CH)— 4-(c-Pr—C≡C)— 4-(c-Pr—CH₂O)— 4-(c-Bu—CH₂O)—4-(c-pentyl-CH₂O)— 4-(HO—N═CH)— 4-(MeO—N═CH)— 4-(HO—N═C(Me))—4-(MeO—N═C(Me))— 4-(MeHC═N—O)— 4-(Me₂C═N—O)— 4-(H₂C═N—O)— 4-(H₂N—N═CH)—4-(MeNH—N═CH)— 4-(Me₂N—N═CH)— 4-(H₂N—N═C(Me))— 4-(MeNH—N═C(Me))—4-(Me₂N—N═C(Me))— 4-(MeHC═N—NH)— 4-(Me₂C═N—NH)— 4-(H₂C═N—NH)—4-(MeHC═N—N(Me))— 4-(Me₂C═N—N(Me))— 4-(H₂C═N—N(Me))— 3-(HC≡CCH₂O)—3-(MeC≡CCH₂O)— 3-(HC≡CCH₂CH₂O)— 3-(MeC≡CCH₂CH₂O)— 3-(H₂C═CHCH₂O)—3-(MeHC═CHCH₂O)— 3-(ClHC═CHCH₂O)— 3-(Cl₂C═CHCH₂O)— 3-(HC≡C(Me)CHO)—3-(H₂C═C(Me)CHO)— 3-(H₂C═CHCH(Me)O)— 3-(MeHC═CHCH(Me)O)— 3-n-butoxy3-i-butoxy 3-s-butoxy 3-n-pentoxy 3-i-pentoxy 3-s-pentoxy3-(c-Pr—HC═CHCH₂O)— 3-(c-Pr—C≡CCH₂O)— 3-(c-Pr—HC═CH)— 3-(c-Pr—C≡C)—3-(c-Pr—CH₂O)— 3-(c-Bu—CH₂O)— 3-(c-pentyl-CH₂O)— 3-(HO—N═CH)—3-(MeO—N═CH)— 3-(HO—N═C(Me))— 3-(MeO—N═C(Me))— 3-(MeHC═N—O)—3-(Me₂C═N—O)— 3-(H₂C═N—O)— 3-(H₂N—N═CH)— 3-(MeNH—N═CH)— 3-(Me₂N—N═CH)—3-(H₂N—N═C(Me))— 3-(MeNH—N═C(Me))— 3-(Me₂N—N═C(Me))— 3-(MeHC═N—NH)—3-(Me₂C═N—NH)— 3-(H₂C═N—NH)— 3-(MeHC═N—N(Me))— 3-(Me₂C═N—N(Me))—3-(H₂C═N—N(Me))— 3-CF₃-1H-pyrazol-1-yl 3-Me-1H-pyrazol-1-yl3-F-1H-pyrazol-1-yl 3-Br-1H-pyrazol-1-yl 4-CF₃-1H-pyrazol-1-yl4-Me-1H-pyrazol-1-yl 4-F-1H-pyrazol-1-yl 4-Br-1H-pyrazol-1-yl5-CF₃-1H-pyrazol-1-yl 5-Me-1H-pyrazol-1-yl 5-F-1H-pyrazol-1-yl5-Br-1H-pyrazol-1-yl 3-CHF₂-1H-pyrazol-1-yl 3-Et-1H-pyrazol-1-yl3-C1-1H-pyrazol-1-yl 3-I-1H-pyrazol-1-yl 4-CHF₂-1H-pyrazol-1-yl3-Et-1H-pyrazol-1-yl 4-Cl-1H-pyrazol-1-yl 4-I-1H-pyrazol-1-yl5-CHF₂-1H-pyrazol-1-yl 3-Et-1H-pyrazol-1-yl 5-C1-1H-pyrazol-1-yl5-I-pyrazol-1-yl 1H-pyrazol-1-yl 1H-1,2,3-triazol-1-yl1H-1,2,3-triazol-1-yl 1H-1,2,3-triazol-2-yl 1H-pyrrol-1-yl1-Me-1H-pyrazol-3-yl 1-CF₃-1H-pyrazol-3-yl

The present disclosure also includes Tables 1B through 215B, each ofwhich is constructed the same as Table 2 above, except that the rowheading in Table 2 (i.e. “Q² is 2,4,6-tri-F-Ph, (R^(3a))_(p) is2,6-di-F”) is replaced with the respective row headings shown below. ForExample, in Table 1B the row heading is “Q² is 2,4,6-tri-F-Ph,(R^(3a))_(p) is 2-F”, and R^(3b) is as defined in Table 2 above. Thus,the first entry in Table 1B specifically discloses5-[2-fluoro-4-(-propyn-1-yloxy)phenyl]-1,3-dimethyl-α-(2,4,6-trifluorophenyl)-1H-pyrazol-4-methanol.Tables 2B through 215B are constructed similarly.

Table Row Heading  1B Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-F.  2B Q²is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-Cl.  3B Q² is 2,4,6-tri-F—Ph,(R^(3a))_(p) is 2-Br.  4B Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-Me. 5B Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  6B Q² is2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  7B Q² is 2,4,6-tri-F—Ph,(R^(3a))_(p) is 2,6-di-Cl.  8B Q² is 2,6-di-F—Ph, (R^(3a))_(p) is2,6-di-F.  9B Q² is 2,6-di-F—Ph, (R^(3a))_(p) is 2-F.  10B Q² is2,6-di-F—Ph, (R^(3a))_(p) is 2-Cl.  11B Q² is 2,6-di-F—Ph, (R^(3a))_(p)is 2-Br.  12B Q² is 2,6-di-F—Ph, (R^(3a))_(p) is 2-Me.  13B Q² is2,6-di-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  14B Q² is 2,6-di-F—Ph,(R^(3a))_(p) is 2-Cl, 6-F.  15B Q² is 2,6-di-F—Ph, (R^(3a))_(p) is2,6-di-Cl.  16B Q² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2,6-di-F.  17BQ² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-F.  18B Q² is2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-Cl.  19B Q² is 2,6-di-F-4-MeO—Ph,(R^(3a))_(p) is 2-Br.  20B Q² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is2-Me.  21B Q² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  22B Q²is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  23B Q² is2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2,6-di-Cl.  24B Q² is2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2,6-di-F.  25B Q² is 2,6-di-F-4-Me—Ph,(R^(3a))_(p) is 2-F.  26B Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2-Cl. 27B Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2-Br.  28B Q² is2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2-Me.  29B Q² is 2,6-di-F-4-Me—Ph,(R^(3a))_(p) is 2-F, 6-Cl  30B Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is2-Cl, 6-F.  31B Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2,6-di-Cl.  32BQ² is 2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2,6-di-F.  33B Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-F.  34B Q² is 2,6-di-F-4-CN—Ph,(R^(3a))_(p) is 2-Cl.  35B Q² is 2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-Br. 36B Q² is 2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-Me.  37B Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  38B Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  39B Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2,6-di-Cl.  40B Q² is2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2,6-di-F.  41B Q² is 2,6-di-F-4-Cl—Ph,(R^(3a))_(p) is 2-F.  42B Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2-Cl. 43B Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2-Br.  44B Q² is2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2-Me.  45B Q² is 2,6-di-F-4-Cl—Ph,(R^(3a))_(p) is 2-F, 6-Cl.  46B Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is2-Cl, 6-F.  47B Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2,6-di-Cl.  48BQ² is 2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2,6-di-F.  49B Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-F.  50B Q² is 2,6-di-F-4-Br—Ph,(R^(3a))_(p) is 2-Cl.  51B Q² is 2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-Br. 52B Q² is 2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-Me.  53B Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  54B Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  55B Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2,6-di-Cl.  56B Q² is 2,4-di-F—Ph,(R^(3a))_(p) is 2,6-di-F.  57B Q² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-F. 58B Q² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-Cl.  59B Q² is 2,4-di-F—Ph,(R^(3a))_(p) is 2-Br.  60B Q² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-Me  61BQ² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  62B Q² is 2,4-di-F—Ph,(R^(3a))_(p) is 2-Cl, 6-F.  63B Q² is 2,4-di-F—Ph, (R^(3a))_(p) is2,6-di-Cl  64B Q² is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2,6-di-F.  65B Q²is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-F.  66B Q² is 2,4-di-F-6-Cl—Ph,(R^(3a))_(p) is 2-Cl.  67B Q² is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-Br. 68B Q² is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-Me.  69B Q² is2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  70B Q² is2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  71B Q² is2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2,6-di-Cl.  72B Q² is2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2,6-di-F  73B Q² is 2,4-di-F-6-Br—Ph,(R^(3a))_(p) is 2-F.  74B Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2-Cl. 75B Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2-Br.  76B Q² is2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2-Me.  77B Q² is 2,4-di-F-6-Br—Ph,(R^(3a))_(p) is 2-F, 6-Cl.  78B Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is2-Cl, 6-F.  79B Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2,6-di-Cl.  80BQ² is 2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-F.  81B Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-F.  82B Q² is 2-Cl-4-Me-6-F—Ph,(R^(3a))_(p) is 2-Cl.  83B Q² is 2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Br. 84B Q² is 2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Me.  85B Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  86B Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  87B Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl.  88B Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-F.  89B Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F.  90B Q² is 2-Cl-4-MeO-6-F—Ph,(R^(3a))_(p) is 2-Cl.  91B Q² is 2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is2-Br.  92B Q² is 2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Me.  93B Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  94B Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  95B Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl.  96B Q² is2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-F.  97B Q² is 2-Br-4-Me-6-F—Ph,(R^(3a))_(p) is 2-F.  98B Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Cl. 99B Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Br. 100B Q² is2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Me 101B Q² is 2-Br-4-Me-6-F—Ph,(R^(3a))_(p) is 2-F, 6-Cl. 102B Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is2-Cl, 6-F. 103B Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl. 104BQ² is 2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-F. 105B Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F. 106B Q² is 2-Br-4-MeO-6-F—Ph,(R^(3a))_(p) is 2-Cl. 107B Q² is 2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is2-Br. 108B Q² is 2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Me. 109B Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl. 110B Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F. 111B Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl. 112B Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2,6-di-F. 113B Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-F. 114B Q² is 2,6-di-Cl-4-Me—Ph,(R^(3a))_(p) is 2-Cl. 115B Q² is 2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is2-Br. 116B Q² is 2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-Me. 117B Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-F, 6-Cl 118B Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-Cl, 6-F. 119B Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2,6-di-Cl. 120B Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2,6-di-F. 121B Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-F. 122B Q² is 2,6-di-Br-4-Me—Ph,(R^(3a))_(p) is 2-Cl. 123B Q² is 2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is2-Br. 124B Q² is 2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-Me. 125B Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-F, 6-Cl. 126B Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-Cl, 6-F. 127B Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2,6-di-Cl. 128B Q² is2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2,6-di-F. 129B Q² is 2,4,6-tri-Cl—Ph,(R^(3a))_(p) is 2-F. 130B Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2-Cl.131B Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2-Br. 132B Q² is2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2-Me. 133B Q² is 2,4,6-tri-Cl—Ph,(R^(3a))_(p) is 2-F, 6-Cl. 134B Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is2-Cl, 6-F. 135B Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2,6-di-Cl. 136BQ² is 2-Cl-4-F, (R^(3a))_(p) is 2,6-di-F. 137B Q² is 2-Cl-4-F,(R^(3a))_(p) is 2-F. 138B Q² is 2-Cl-4-F, (R^(3a))_(p) is 2-Cl. 139B Q²is 2-Cl-4-F, (R^(3a))_(p) is 2-Br. 140B Q² is 2-Cl-4-F, (R^(3a))_(p) is2-Me. 141B Q² is 2-Cl-4-F, (R^(3a))_(p) is 2-F, 6-Cl 142B Q² is2-Cl-4-F, (R^(3a))_(p) is 2-Cl, 6-F 143B Q² is 2-Cl-4-F, (R^(3a))_(p) is2,6-di-Cl. 144B Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2,6-di-F. 145B Q² is2-Cl-4-Me, (R^(3a))_(p) is 2-F. 146B Q² is 2-Cl-4-Me, (R^(3a))_(p) is2-Cl. 147B Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2-Br. 148B Q² is 2-Cl-4-Me,(R^(3a))_(p) is 2-Me. 149B Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2-F, 6-Cl.150B Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2-Cl, 6-F. 151B Q² is 2-Cl-4-Me,(R^(3a))_(p) is 2,6-di-Cl. 152B Q² is 2-Cl-4-MeO, (R^(3a))_(p) is2,6-di-F. 153B Q² is 2-Cl-4-MeO, (R^(3a))_(p) is 2-F 154B Q² is2-Cl-4-MeO, (R^(3a))_(p) is 2-Cl. 155B Q² is 2-Cl-4-MeO, (R^(3a))_(p) is2-Br. 156B Q² is 2-Cl-4-MeO, (R^(3a))_(p) is 2-Me . . . 157B Q² is2-Cl-4-MeO, (R^(3a))_(p) is 2-F, 6-Cl. 158B Q² is 2-Cl-4-MeO,(R^(3a))_(p) is 2-Cl, 6-F. 159B Q² is 2-Cl-4-MeO, (R^(3a))_(p) is2,6-di-Cl. 160B Q² is 2-Br-4-F, (R^(3a))_(p) is 2,6-di-F. 161B Q² is2-Br-4-F, (R^(3a))_(p) is 2-F. 162B Q² is 2-Br-4-F, (R^(3a))_(p) is2-Cl. 163B Q² is 2-Br-4-F, (R^(3a))_(p) is 2-Br. 164B Q² is 2-Br-4-F,(R^(3a))_(p) is 2-Me. 165B Q² is 2-Br-4-F, (R^(3a))_(p) is 2-F, 6-Cl.166B Q² is 2-Br-4-F, (R^(3a))_(p) is 2-Cl, 6-F. 167B Q² is 2-Br-4-F,(R^(3a))_(p) is 2,6-di-Cl. 168B Q² is 2-Br-4-Me, (R^(3a))_(p) is2,6-di-F. 169B Q² is 2-Br-4-Me, (R^(3a))_(p) is 2-F. 170B Q² is2-Br-4-Me, (R^(3a))_(p) is 2-Cl. 171B Q² is 2-Br-4-Me, (R^(3a))_(p) is2-Br. 172B Q² is 2-Br-4-Me, (R^(3a))_(p) is 2-Me. 173B Q² is 2-Br-4-Me,(R^(3a))_(p) is 2-F, 6-Cl. 174B Q² is 2-Br-4-Me, (R^(3a))_(p) is 2-Cl,6-F. 175B Q² is 2-Br-4-Me, (R^(3a))_(p) is 2,6-di-Cl. 176B Q² is2-Br-4-MeO, (R^(3a))_(p) is 2,6-di-F. 177B Q² is 2-Br-4-MeO,(R^(3a))_(p) is 2-F. 178B Q² is 2-Br-4-MeO, (R^(3a))_(p) is 2-Cl. 179BQ² is 2-Br-4-MeO, (R^(3a))_(p) is 2-Br. 180B Q² is 2-Br-4-MeO,(R^(3a))_(p) is 2-Me. 181B Q² is 2-Br-4-MeO, (R^(3a))_(p) is 2-F, 6-Cl.182B Q² is 2-Br-4-MeO, (R^(3a))_(p) is 2-Cl, 6-F. 183B Q² is 2-Br-4-MeO,(R^(3a))_(p) is 2,6-di-Cl. 184B Q² is 2,4-di-Cl, (R^(3a))_(p) is2,6-di-F. 185B Q² is 2,4-di-Cl, (R^(3a))_(p) is 2-F. 186B Q² is2,4-di-Cl, (R^(3a))_(p) is 2-Cl. 187B Q² is 2,4-di-Cl, (R^(3a))_(p) is2-Br. 188B Q² is 2,4-di-Cl, (R^(3a))_(p) is 2-Me. 189B Q² is 2,4-di-Cl,(R^(3a))_(p) is 2-F, 6-Cl. 190B Q² is 2,4-di-Cl, (R^(3a))_(p) is 2-Cl,6-F. 191B Q² is 2,4-di-Cl, (R^(3a))_(p) is 2,6-di-Cl. 192B Q² is2,6-di-Cl, (R^(3a))_(p) is 2,6-di-F. 193B Q² is 2,6-di-Cl, (R^(3a))_(p)is 2-F. 194B Q² is 2,6-di-Cl, (R^(3a))_(p) is 2-Cl. 195B Q² is2,6-di-Cl, (R^(3a))_(p) is 2-Br. 196B Q² is 2,6-di-Cl, (R^(3a))_(p) is2-Me. 197B Q² is 2,6-di-Cl, (R^(3a))_(p) is 2-F, 6-Cl. 198B Q² is2,6-di-Cl, (R^(3a))_(p) is 2-Cl, 6-F. 199B Q² is 2,6-di-Cl, (R^(3a))_(p)is 2,6-di-Cl. 200B Q² is 2,4-di-Me, (R^(3a))_(p) is 2,6-di-F. 201B Q² is2,4-di-Me, (R^(3a))_(p) is 2-F. 202B Q² is 2,4-di-Me, (R^(3a))_(p) is2-Cl. 203B Q² is 2,4-di-Me, (R^(3a))_(p) is 2-Br. 204B Q² is 2,4-di-Me,(R^(3a))_(p) is 2-Me. 205B Q² is 2,4-di-Me, (R^(3a))_(p) is 2-F, 6-Cl.206B Q² is 2,4-di-Me, (R^(3a))_(p) is 2-Cl, 6-F. 207B Q² is 2,4-di-Me,(R^(3a))_(p) is 2,6-di-Cl. 208B Q² is 2,6-di-Me, (R^(3a))_(p) is2,6-di-F. 209B Q² is 2,6-di-Me, (R^(3a))_(p) is 2-F. 210B Q² is2,6-di-Me, (R^(3a))_(p) is 2-Cl 211B Q² is 2,6-di-Me, (R^(3a))_(p) is2-Br. 212B Q² is 2,6-di-Me, (R^(3a))_(p) is 2-Me. 213B Q² is 2,6-di-Me,(R^(3a))_(p) is 2-F, 6-Cl. 214B Q² is 2,6-di-Me, (R^(3a))_(p) is 2-Cl,6-F. 215B Q² is 2,6-di-Me, (R^(3a))_(p) is 2,6-di-Cl.

TABLE 3

Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2,6-di-F. R^(3b) R^(3b) R^(3b)R^(3b) 4-(HC≡CCH₂O)— 4-(MeC≡CCH₂O)— 4-(HC≡CCH₂CH₂O)— 4-(MeC≡CCH₂CH₂O)—4-(H₂C═CHCH₂O)— 4-(MeHC═CCH₂O)— 4-(ClHC═CHCH₂O)— 4-(Cl₂C═CHCH₂O)—4-(HC≡C(Me)CHO)— 4-(H₂C═C(Me)CHO)— 4-(H₂C═CHCH(Me)O)—4-(MeHC═CHCH(Me)O)— 4-n-butoxy 4-i-butoxy 4-s-butoxy 4-n-pentoxy4-i-pentoxy 4-s-pentoxy 4-(c-Pr—HC═CHCH₂O)— 4-(c-Pr—C≡CCH₂O)—4-(c-Pr—HC═CH)— 4-(c-Pr—C≡C)— 4-(c-Pr—CH₂O)— 4-(c-Bu—CH₂O)—4-(c-pentyl-CH₂O)— 4-(HO—N═CH)— 4-(MeO—N═CH)— 4-(HO—N═C(Me))—4-(MeO—N═C(Me))— 4-(MeHC═N—O)— 4-(Me₂C═N—O)— 4-(H₂C═N—O)— 4-(H₂N—N═CH)—4-(MeNH—N═CH)— 4-(Me₂N—N═CH)— 4-(H₂N—N═C(Me))— 4-(MeNH—N═C(Me))—4-(Me₂N—N═C(Me))— 4-(MeHC═N—NH)— 4-(Me₂C═N—NH)— 4-(H₂C═N—NH)—4-(MeHC═N—N(Me))— 4-(Me₂C═N—N(Me))— 4-(H₂C═N—N(Me))— 3-(HC≡CCH₂O)—3-(MeC≡CCH₂O)— 3-(HC≡CCH₂CH₂O)— 3-(MeC≡CCH₂CH₂O)— 3-(H₂C═CHCH₂O)—3-(MeHC═CHCH₂O)— 3-(ClHC═CHCH₂O)— 3-(Cl₂C═CHCH₂O)— 3-(HC≡C(Me)CHO)—3-(H₂C═C(Me)CHO)— 3-(H₂C═CHCH(Me)O)— 3-(MeHC═CHCH(Me)O)— 3-n-butoxy3-i-butoxy 3-s-butoxy 3-n-pentoxy 3-i-pentoxy 3-s-pentoxy3-(c-Pr—HC═CHCH₂O)— 3-(c-Pr—C≡CCH₂O)— 3-(c-Pr—HC═CH)— 3-(c-Pr—C≡C)—3-(c-Pr—CH₂O)— 3-(c-Bu—CH₂O)— 3-(c-pentyl-CH₂O)— 3-(HO—N═CH)—3-(MeO—N═CH)— 3-(HO—N═C(Me))— 3-(MeO—N═C(Me))— 3-(MeHC═N—O)—3-(Me₂C═N—O)— 3-(H₂C═N—O)— 3-(H₂N—N═CH)— 3-(MeNH—N═CH)— 3-(Me₂N—N═CH)—3-(H₂N—N═C(Me))— 3-(MeNH—N═C(Me))— 3-(Me₂N—N═C(Me))— 3-(MeHC═N—NH)—3-(Me₂C═N—NH)— 3-(H₂C═N—NH)— 3-(MeHC═N—N(Me))— 3-(Me₂C═N—N(Me))—3-(H₂C═N—N(Me))— 3-CF₃-1H-pyrazol-1-yl 3-Me-1H-pyrazol-1-yl3-F-1H-pyrazol-1-yl 3-Br-1H-pyrazol-1-yl 4-CF₃-1H-pyrazol-1-yl4-Me-1H-pyrazol-1-yl 4-F-1H-pyrazol-1-yl 4-Br-1H-pyrazol-1-yl5-CF₃-1H-pyrazol-1-yl 5-Me-1H-pyrazol-1-yl 5-F-1H-pyrazol-1-yl5-Br-1H-pyrazol-1-yl 3-CHF₂-1H-pyrazol-1-yl 3-Et-1H-pyrazol-1-yl3-C1-1H-pyrazol-1-yl 3-I-1H-pyrazol-1-yl 4-CHF₂-1H-pyrazol-1-yl3-Et-1H-pyrazol-1-yl 4-Cl-1H-pyrazol-1-yl 4-I-1H-pyrazol-1-yl5-CHF₂-1H-pyrazol-1-yl 3-Et-1H-pyrazol-1-yl 5-C1-1H-pyrazol-1-yl5-I-pyrazol-1-yl 1H-pyrazol-1-yl 1H-1,2,3-triazol-1-yl1H-1,2,3-triazol-1-yl 1H-1,2,3-triazol-2-yl 1H-pyrrol-1-yl1-Me-1H-pyrazol-3-yl 1-CF₃-1H-pyrazol-3-yl

The present disclosure also includes Tables 1C through 215C, each ofwhich is constructed the same as Table 3 above, except that the rowheading in Table 3 (i.e. “Q² is 2,4,6-tri-F-Ph, (R^(3a))_(p) is2,6-di-F”) is replaced with the respective row headings shown below. ForExample, in Table 1C the row heading is “Q² is 2,4,6-tri-F-Ph,(R^(3a))_(p) is 2-F”, and R^(3b) is as defined in Table 3 above. Thus,the first entry in Table 1C specifically discloses5-[2-fluoro-4-(-propyn-1-yloxy)phenyl]-1,3-dimethyl-4-[(2,4,6-trifluorophenyl)-methyl]-1H-pyrazole.Tables 2C through 215C are constructed similarly.

Table Row Heading  1C Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-F.  2C Q²is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-Cl.  3C Q² is 2,4,6-tri-F—Ph,(R^(3a))_(p) is 2-Br.  4C Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-Me. 5C Q² is 2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  6C Q² is2,4,6-tri-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  7C Q² is 2,4,6-tri-F—Ph,(R^(3a))_(p) is 2,6-di-Cl.  8C Q² is 2,6-di-F—Ph, (R^(3a))_(p) is2,6-di-F.  9C Q² is 2,6-di-F—Ph, (R^(3a))_(p) is 2-F.  10C Q² is2,6-di-F—Ph, (R^(3a))_(p) is 2-Cl.  11C Q² is 2,6-di-F—Ph, (R^(3a))_(p)is 2-Br.  12C Q² is 2,6-di-F—Ph, (R^(3a))_(p) is 2-Me.  13C Q² is2,6-di-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  14C Q² is 2,6-di-F—Ph,(R^(3a))_(p) is 2-Cl, 6-F.  15C Q² is 2,6-di-F—Ph, (R^(3a))_(p) is2,6-di-Cl.  16C Q² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2,6-di-F.  17CQ² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-F.  18C Q² is2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-Cl.  19C Q² is 2,6-di-F-4-MeO—Ph,(R^(3a))_(p) is 2-Br.  20C Q² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is2-Me.  21C Q² is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  22C Q²is 2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  23C Q² is2,6-di-F-4-MeO—Ph, (R^(3a))_(p) is 2,6-di-Cl.  24C Q² is2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2,6-di-F.  25C Q² is 2,6-di-F-4-Me—Ph,(R^(3a))_(p) is 2-F.  26C Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2-Cl. 27C Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2-Br.  28C Q² is2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2-Me.  29C Q² is 2,6-di-F-4-Me—Ph,(R^(3a))_(p) is 2-F, 6-Cl  30C Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is2-Cl, 6-F.  31C Q² is 2,6-di-F-4-Me—Ph, (R^(3a))_(p) is 2,6-di-Cl.  32CQ² is 2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2,6-di-F.  33C Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-F.  34C Q² is 2,6-di-F-4-CN—Ph,(R^(3a))_(p) is 2-Cl.  35C Q² is 2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-Br. 36C Q² is 2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-Me.  37C Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  38C Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  39C Q² is2,6-di-F-4-CN—Ph, (R^(3a))_(p) is 2,6-di-Cl.  40C Q² is2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2,6-di-F.  41C Q² is 2,6-di-F-4-Cl—Ph,(R^(3a))_(p) is 2-F.  42C Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2-Cl. 43C Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2-Br.  44C Q² is2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2-Me.  45C Q² is 2,6-di-F-4-Cl—Ph,(R^(3a))_(p) is 2-F, 6-Cl.  46C Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is2-Cl, 6-F.  47C Q² is 2,6-di-F-4-Cl—Ph, (R^(3a))_(p) is 2,6-di-Cl.  48CQ² is 2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2,6-di-F.  49C Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-F.  50C Q² is 2,6-di-F-4-Br—Ph,(R^(3a))_(p) is 2-Cl.  51C Q² is 2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-Br. 52C Q² is 2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-Me.  53C Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  54C Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  55C Q² is2,6-di-F-4-Br—Ph, (R^(3a))_(p) is 2,6-di-Cl.  56C Q² is 2,4-di-F—Ph,(R^(3a))_(p) is 2,6-di-F.  57C Q² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-F. 58C Q² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-Cl.  59C Q² is 2,4-di-F—Ph,(R^(3a))_(p) is 2-Br.  60C Q² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-Me  61CQ² is 2,4-di-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  62C Q² is 2,4-di-F—Ph,(R^(3a))_(p) is 2-Cl, 6-F.  63C Q² is 2,4-di-F—Ph, (R^(3a))_(p) is2,6-di-Cl  64C Q² is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2,6-di-F.  65C Q²is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-F.  66C Q² is 2,4-di-F-6-Cl—Ph,(R^(3a))_(p) is 2-Cl.  67C Q² is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-Br. 68C Q² is 2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-Me.  69C Q² is2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  70C Q² is2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  71C Q² is2,4-di-F-6-Cl—Ph, (R^(3a))_(p) is 2,6-di-Cl.  72C Q² is2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2,6-di-F  73C Q² is 2,4-di-F-6-Br—Ph,(R^(3a))_(p) is 2-F.  74C Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2-Cl. 75C Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2-Br.  76C Q² is2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2-Me.  77C Q² is 2,4-di-F-6-Br—Ph,(R^(3a))_(p) is 2-F, 6-Cl.  78C Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is2-Cl, 6-F.  79C Q² is 2,4-di-F-6-Br—Ph, (R^(3a))_(p) is 2,6-di-Cl.  80CQ² is 2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-F.  81C Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-F.  82C Q² is 2-Cl-4-Me-6-F—Ph,(R^(3a))_(p) is 2-Cl.  83C Q² is 2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Br. 84C Q² is 2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Me.  85C Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  86C Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  87C Q² is2-Cl-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl.  88C Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-F.  89C Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F.  90C Q² is 2-Cl-4-MeO-6-F—Ph,(R^(3a))_(p) is 2-Cl.  91C Q² is 2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is2-Br.  92C Q² is 2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Me.  93C Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl.  94C Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F.  95C Q² is2-Cl-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl.  96C Q² is2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-F.  97C Q² is 2-Br-4-Me-6-F—Ph,(R^(3a))_(p) is 2-F.  98C Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Cl. 99C Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Br. 100C Q² is2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2-Me 101C Q² is 2-Br-4-Me-6-F—Ph,(R^(3a))_(p) is 2-F, 6-Cl. 102C Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is2-Cl, 6-F. 103C Q² is 2-Br-4-Me-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl. 104CQ² is 2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-F. 105C Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F. 106C Q² is 2-Br-4-MeO-6-F—Ph,(R^(3a))_(p) is 2-Cl. 107C Q² is 2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is2-Br. 108C Q² is 2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Me. 109C Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-F, 6-Cl. 110C Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2-Cl, 6-F. 111C Q² is2-Br-4-MeO-6-F—Ph, (R^(3a))_(p) is 2,6-di-Cl. 112C Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2,6-di-F. 113C Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-F. 114C Q² is 2,6-di-Cl-4-Me—Ph,(R^(3a))_(p) is 2-Cl. 115C Q² is 2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is2-Br. 116C Q² is 2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-Me. 117C Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-F, 6-Cl 118C Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2-Cl, 6-F. 119C Q² is2,6-di-Cl-4-Me—Ph, (R^(3a))_(p) is 2,6-di-Cl. 120C Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2,6-di-F. 121C Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-F. 122C Q² is 2,6-di-Br-4-Me—Ph,(R^(3a))_(p) is 2-Cl. 123C Q² is 2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is2-Br. 124C Q² is 2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-Me. 125C Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-F, 6-Cl. 126C Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2-Cl, 6-F. 127C Q² is2,6-di-Br-4-Me—Ph, (R^(3a))_(p) is 2,6-di-Cl. 128C Q² is2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2,6-di-F. 129C Q² is 2,4,6-tri-Cl—Ph,(R^(3a))_(p) is 2-F. 130C Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2-Cl.131C Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2-Br. 132C Q² is2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2-Me. 133C Q² is 2,4,6-tri-Cl—Ph,(R^(3a))_(p) is 2-F, 6-Cl. 134C Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is2-Cl, 6-F. 135C Q² is 2,4,6-tri-Cl—Ph, (R^(3a))_(p) is 2,6-di-Cl. 136CQ² is 2-Cl-4-F, (R^(3a))_(p) is 2,6-di-F. 137C Q² is 2-Cl-4-F,(R^(3a))_(p) is 2-F. 138C Q² is 2-Cl-4-F, (R^(3a))_(p) is 2-Cl. 139C Q²is 2-Cl-4-F, (R^(3a))_(p) is 2-Br. 140C Q² is 2-Cl-4-F, (R^(3a))_(p) is2-Me. 141C Q² is 2-Cl-4-F, (R^(3a))_(p) is 2-F, 6-Cl 142C Q² is2-Cl-4-F, (R^(3a))_(p) is 2-Cl, 6-F 143C Q² is 2-Cl-4-F, (R^(3a))_(p) is2,6-di-Cl. 144C Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2,6-di-F. 145C Q² is2-Cl-4-Me, (R^(3a))_(p) is 2-F. 146C Q² is 2-Cl-4-Me, (R^(3a))_(p) is2-Cl. 147C Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2-Br. 148C Q² is 2-Cl-4-Me,(R^(3a))_(p) is 2-Me. 149C Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2-F, 6-Cl.150C Q² is 2-Cl-4-Me, (R^(3a))_(p) is 2-Cl, 6-F. 151C Q² is 2-Cl-4-Me,(R^(3a))_(p) is 2,6-di-Cl. 152C Q² is 2-Cl-4-MeO, (R^(3a))_(p) is2,6-di-F. 153C Q² is 2-Cl-4-MeO, (R^(3a))_(p) is 2-F 154C Q² is2-Cl-4-MeO, (R^(3a))_(p) is 2-Cl. 155C Q² is 2-Cl-4-MeO, (R^(3a))_(p) is2-Br. 156C Q² is 2-Cl-4-MeO, (R^(3a))_(p) is 2-Me . . . 157C Q² is2-Cl-4-MeO, (R^(3a))_(p) is 2-F, 6-Cl. 158C Q² is 2-Cl-4-MeO,(R^(3a))_(p) is 2-Cl, 6-F. 159C Q² is 2-Cl-4-MeO, (R^(3a))_(p) is2,6-di-Cl. 160C Q² is 2-Br-4-F, (R^(3a))_(p) is 2,6-di-F. 161C Q² is2-Br-4-F, (R^(3a))_(p) is 2-F. 162C Q² is 2-Br-4-F, (R^(3a))_(p) is2-Cl. 163C Q² is 2-Br-4-F, (R^(3a))_(p) is 2-Br. 164C Q² is 2-Br-4-F,(R^(3a))_(p) is 2-Me. 165C Q² is 2-Br-4-F, (R^(3a))_(p) is 2-F, 6-Cl.166C Q² is 2-Br-4-F, (R^(3a))_(p) is 2-Cl, 6-F. 167C Q² is 2-Br-4-F,(R^(3a))_(p) is 2,6-di-Cl. 168C Q² is 2-Br-4-Me, (R^(3a))_(p) is2,6-di-F. 169C Q² is 2-Br-4-Me, (R^(3a))_(p) is 2-F. 170C Q² is2-Br-4-Me, (R^(3a))_(p) is 2-Cl. 171C Q² is 2-Br-4-Me, (R^(3a))_(p) is2-Br. 172C Q² is 2-Br-4-Me, (R^(3a))_(p) is 2-Me. 173C Q² is 2-Br-4-Me,(R^(3a))_(p) is 2-F, 6-Cl. 174C Q² is 2-Br-4-Me, (R^(3a))_(p) is 2-Cl,6-F. 175C Q² is 2-Br-4-Me, (R^(3a))_(p) is 2,6-di-Cl. 176C Q² is2-Br-4-MeO, (R^(3a))_(p) is 2,6-di-F. 177C Q² is 2-Br-4-MeO,(R^(3a))_(p) is 2-F. 178C Q² is 2-Br-4-MeO, (R^(3a))_(p) is 2-Cl. 179CQ² is 2-Br-4-MeO, (R^(3a))_(p) is 2-Br. 180C Q² is 2-Br-4-MeO,(R^(3a))_(p) is 2-Me. 181C Q² is 2-Br-4-MeO, (R^(3a))_(p) is 2-F, 6-Cl.182C Q² is 2-Br-4-MeO, (R^(3a))_(p) is 2-Cl, 6-F. 183C Q² is 2-Br-4-MeO,(R^(3a))_(p) is 2,6-di-Cl. 184C Q² is 2,4-di-Cl, (R^(3a))_(p) is2,6-di-F. 185C Q² is 2,4-di-Cl, (R^(3a))_(p) is 2-F. 186C Q² is2,4-di-Cl, (R^(3a))_(p) is 2-Cl. 187C Q² is 2,4-di-Cl, (R^(3a))_(p) is2-Br. 188C Q² is 2,4-di-Cl, (R^(3a))_(p) is 2-Me. 189C Q² is 2,4-di-Cl,(R^(3a))_(p) is 2-F, 6-Cl. 190C Q² is 2,4-di-Cl, (R^(3a))_(p) is 2-Cl,6-F. 191C Q² is 2,4-di-Cl, (R^(3a))_(p) is 2,6-di-Cl. 192C Q² is2,6-di-Cl, (R^(3a))_(p) is 2,6-di-F. 193C Q² is 2,6-di-Cl, (R^(3a))_(p)is 2-F. 194C Q² is 2,6-di-Cl, (R^(3a))_(p) is 2-Cl. 195C Q² is2,6-di-Cl, (R^(3a))_(p) is 2-Br. 196C Q² is 2,6-di-Cl, (R^(3a))_(p) is2-Me. 197C Q² is 2,6-di-Cl, (R^(3a))_(p) is 2-F, 6-Cl. 198C Q² is2,6-di-Cl, (R^(3a))_(p) is 2-Cl, 6-F. 199C Q² is 2,6-di-Cl, (R^(3a))_(p)is 2,6-di-Cl. 200C Q² is 2,4-di-Me, (R^(3a))_(p) is 2,6-di-F. 201C Q² is2,4-di-Me, (R^(3a))_(p) is 2-F. 202C Q² is 2,4-di-Me, (R^(3a))_(p) is2-Cl. 203C Q² is 2,4-di-Me, (R^(3a))_(p) is 2-Br. 204C Q² is 2,4-di-Me,(R^(3a))_(p) is 2-Me. 205C Q² is 2,4-di-Me, (R^(3a))_(p) is 2-F, 6-Cl.206C Q² is 2,4-di-Me, (R^(3a))_(p) is 2-Cl, 6-F. 207C Q² is 2,4-di-Me,(R^(3a))_(p) is 2,6-di-Cl. 208C Q² is 2,6-di-Me, (R^(3a))_(p) is2,6-di-F. 209C Q² is 2,6-di-Me, (R^(3a))_(p) is 2-F. 210C Q² is2,6-di-Me, (R^(3a))_(p) is 2-Cl 211C Q² is 2,6-di-Me, (R^(3a))_(p) is2-Br. 212C Q² is 2,6-di-Me, (R^(3a))_(p) is 2-Me. 213C Q² is 2,6-di-Me,(R^(3a))_(p) is 2-F, 6-Cl. 214C Q² is 2,6-di-Me, (R^(3a))_(p) is 2-Cl,6-F. 215C Q² is 2,6-di-Me, (R^(3a))_(p) is 2,6-di-Cl.

Formulation/Utility

A compound of this invention will generally be used as a fungicidalactive ingredient in a composition, i.e. formulation, with at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents, which serve as a carrier. Theformulation or composition ingredients are selected to be consistentwith the physical properties of the active ingredient, mode ofapplication and environmental factors such as soil type, moisture andtemperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions and/or suspoemulsions)and the like, which optionally can be thickened into gels. The generaltypes of aqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsionand suspo-emulsion. The general types of nonaqueous liquid compositionsare emulsifiable concentrate, microemulsifiable concentrate, dispersibleconcentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, prills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying. Such liquid and solid formulations are formulated to bereadily diluted in the spray medium, usually water. Spray volumes canrange from about one to several thousand liters per hectare, but moretypically are in the range from about ten to several hundred liters perhectare. Sprayable formulations can be tank mixed with water or anothersuitable medium for foliar treatment by aerial or ground application, orfor application to the growing medium of the plant. Liquid and dryformulations can be metered directly into drip irrigation systems ormetered into the furrow during planting. Liquid and solid formulationscan be applied onto seeds of crops and other desirable vegetation asseed treatments before planting to protect developing roots and othersubterranean plant parts and/or foliage through systemic uptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water- 0.001-90 0-99.999 0-15 soluble Granules, Tablets and PowdersOil Dispersions, Suspensions,    1-50 40-99    0-50 Emulsions, Solutions(including Emulsifiable Concentrates) Dusts    1-25 70-99    0-5 Granules and Pellets 0.001-95 5-99.999 0-15 High Strength Compositions  90-99 0-10    0-2 

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol,triethylene glycol, propylene glycol, dipropylene glycol, polypropyleneglycol, propylene carbonate, butylene carbonate, paraffins (e.g., whitemineral oils, normal paraffins, isoparaffins), alkylbenzenes,alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatichydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes,ketones such as cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexylacetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetateand isobornyl acetate, other esters such as alkylated lactate esters,dibasic esters and γ-butyrolactone, and alcohols, which can be linear,branched, saturated or unsaturated, such as methanol, ethanol,n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol,2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol,cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol,cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol and benzylalcohol. Liquid diluents also include glycerol esters of saturated andunsaturated fatty acids (typically C₆-C₂₂), such as plant seed and fruitoils (e.g., oils of olive, castor, linseed, sesame, corn (maize),peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed,coconut and palm kernel), animal-sourced fats (e.g., beef tallow, porktallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquiddiluents also include alkylated fatty acids (e.g., methylated,ethylated, butylated) wherein the fatty acids may be obtained byhydrolysis of glycerol esters from plant and animal sources, and can bepurified by distillation. Typical liquid diluents are described inMarsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyd peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquaternary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids(some of which may be considered to also function as solid diluents,liquid diluents or surfactants). Such formulation auxiliaries andadditives may control: pH (buffers), foaming during processing(antifoams such polyorganosiloxanes), sedimentation of activeingredients (suspending agents), viscosity (thixotropic thickeners),in-container microbial growth (antimicrobials), product freezing(antifreezes), color (dyes/pigment dispersions), wash-off (film formersor stickers), evaporation (evaporation retardants), and otherformulation attributes. Film formers include, for example, polyvinylacetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinylacetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers andwaxes. Examples of formulation auxiliaries and additives include thoselisted in McCutcheon's Volume 2: Functional Materials, annualInternational and North American editions published by McCutcheon'sDivision, The Manufacturing Confectioner Publishing Co.; and PCTPublication WO 03/024222.

The compound of Formula 1 and any other active ingredients are typicallyincorporated into the present compositions by dissolving the activeingredient in a solvent or by grinding in a liquid or dry diluent.Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 μm can be wet milled using media mills toobtain particles with average diameters below 3 μm. Aqueous slurries canbe made into finished suspension concentrates (see, for example, U.S.Pat. No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 jamrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963,pages 8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. No.4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can beprepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, U K, 2000.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Compound numbers referto compounds in Index Table A. Without further elaboration, it isbelieved that one skilled in the art using the preceding description canutilize the present invention to its fullest extent. The followingExamples are, therefore, to be constructed as merely illustrative, andnot limiting of the disclosure in any way whatsoever.

Example A High Strength Concentrate

Compound 2 98.5% silica aerogel 0.5% synthetic amorphous fine silica1.0%

Example B Wettable Powder

Compound 2 65.0% dodecylphenol polyethylene glycol ether 2.0% sodiumligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite(calcined) 23.0%

Example C Granule

Compound 2 10.0% attapulgite granules (low volatile matter, 0.71/0.30mm; 90.0% U.S.S. No. 25-50 sieves)

Example D Extruded Pellet

Compound 2 25.0% anhydrous sodium sulfate 10.0% crude calciumligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0%calcium/magnesium bentonite 59.0%

Example E Emulsifiable Concentrate

Compound 2 10.0% polyoxyethylene sorbitol hexoleate 20.0% C₆-C₁₀ fattyacid methyl ester 70.0%

Example F Microemulsion

Compound 2 5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0%alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%

Example G Seed Treatment

Compound 2 20.00% polyvinylpyrrolidone-vinyl acetate copolymer 5.00%montan acid wax 5.00% calcium ligninsulfonate 1.00%polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol(POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water65.75%

Water-soluble and water-dispersible formulations are typically dilutedwith water to form aqueous compositions before application. Aqueouscompositions for direct applications to the plant or portion thereof(e.g., spray tank compositions) typically at least about 1 ppm or more(e.g., from 1 ppm to 100 ppm) of the compound(s) of this invention.

The compounds of this invention are useful as plant disease controlagents. The present invention therefore further comprises a method forcontrolling plant diseases caused by fungal plant pathogens comprisingapplying to the plant or portion thereof to be protected, or to theplant seed to be protected, an effective amount of a compound of theinvention or a fungicidal composition containing said compound. Thecompounds and/or compositions of this invention provide control ofdiseases caused by a broad spectrum of fungal plant pathogens in theBasidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They areeffective in controlling a broad spectrum of plant diseases,particularly foliar pathogens of ornamental, turf, vegetable, field,cereal, and fruit crops. These pathogens include: Oomycetes, includingPhytophthora diseases such as Phytophthora infestans, Phytophthoramegasperma, Phytophthora parasitica, Phytophthora cinnamomi andPhytophthora capsici, Pythium diseases such as Pythium aphanidermatum,and diseases in the Peronosporaceae family such as Plasmopara viticola,Peronospora spp. (including Peronospora tabacina and Peronosporaparasitica), Pseudoperonospora spp. (including Pseudoperonosporacubensis) and Bremia lactucae; Ascomycetes, including Alternariadiseases such as Alternaria solani and Alternaria brassicae, Guignardiadiseases such as Guignardia bidwell, Venturia diseases such as Venturiainaequalis, Septoria diseases such as Septoria nodorum and Septoriatritici, powdery mildew diseases such as Erysiphe spp. (includingErysiphe graminis and Erysiphe polygoni), Uncinula necatur, Sphaerothecafuliginea, Podosphaera leucotricha and Pseudocercosporellaherpotrichoides, Botrytis diseases such as Botrytis cinerea, Moniliniafructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum,Sclerotinia minor, Magnaporthe grisea, and Phomopsis viticola,Helminthosporium diseases such as Helminthosporium tritici repentis andPyrenophora teres, anthracnose diseases such as Glomerella orColletotrichum spp. (such as Colletotrichum graminicola andColletotrichum orbiculare), and Gaeumannomyces graminis; Basidiomycetes,including rust diseases caused by Puccinia spp. (such as Pucciniarecondita, Puccinia striiformis, Puccinia hordei, Puccinia graminis andPuccinia arachidis), Hemileia vastatrix and Phakopsora pachyrhizi; otherpathogens including Rutstroemia floccosum (also known as Sclerotiniahomoeocarpa); Rhizoctonia spp. (such as Rhizoctonia solani); Fusariumdiseases such as Fusarium roseum, Fusarium graminearum and Fusariumoxysporum Verticillium dahliae; Sclerotium rolfsii; Rynchosporiumsecalis; Cercosporidium personatum, Cercospora arachidicola andCercospora beticola; Rhizopus spp. (such as Rhizopus stolonifer);Aspergillus spp. (such as Aspergillus flavus and Aspergillusparasiticus); and other genera and species closely related to thesepathogens. In addition to their fungicidal activity, the compositions orcombinations also have activity against bacteria such as Erwiniaamylovora, Xanthomonas campestris, Pseudomonas syringae, and otherrelated species. Furthermore, the compounds of this invention are usefulin treating postharvest diseases of fruits and vegetables caused byfungi and bacteria. These infections can occur before, during and afterharvest. For example, infections can occur before harvest and thenremain dormant until some point during ripening (e.g., host beginstissue changes in such a way that infection can progress); alsoinfections can arise from surface wounds created by mechanical or insectinjury. In this respect, the compounds of this invention can reducelosses (i.e. losses resulting from quantity and quality) due topostharvest diseases which may occur at any time from harvest toconsumption. Treatment of postharvest diseases with compounds of theinvention can increase the period of time during which perishable edibleplant parts (e.g, fruits, seeds, foliage, stems, bulbs, tubers) can bestored refrigerated or un-refrigerated after harvest, and remain edibleand free from noticeable or harmful degradation or contamination byfungi or other microorganisms. Treatment of edible plant parts before orafter harvest with compounds of the invention can also decrease theformation of toxic metabolites of fungi or other microorganisms, forexample, mycotoxins such as aflatoxins.

Plant disease control is ordinarily accomplished by applying aneffective amount of a compound of this invention either pre- orpost-infection, to the portion of the plant to be protected such as theroots, stems, foliage, fruits, seeds, tubers or bulbs, or to the media(soil or sand) in which the plants to be protected are growing. Thecompounds can also be applied to seeds to protect the seeds andseedlings developing from the seeds. The compounds can also be appliedthrough irrigation water to treat plants. Control of postharvestpathogens which infect the produce before harvest is typicallyaccomplished by field application of a compound of this invention, andin cases where infection occurs after harvest the compounds can beapplied to the harvested crop as dips, sprays, fumigants, treated wrapsand box liners.

Rates of application for these compounds (i.e. a fungicidally effectiveamount) can be influenced by factors such as the plant diseases to becontrolled, the plant species to be protected, ambient moisture andtemperature and should be determined under actual use conditions. Oneskilled in the art can easily determine through simple experimentationthe fungicidally effective amount necessary for the desired level ofplant disease control. Foliage can normally be protected when treated ata rate of from less than about 1 g/ha to about 5,000 g/ha of activeingredient. Seed and seedlings can normally be protected when seed istreated at a rate of from about 0.1 to about 10 g per kilogram of seed.

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including fungicides,insecticides, nematocides, bactericides, acaricides, herbicides,herbicide safeners, growth regulators such as insect molting inhibitorsand rooting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, plant nutrients, otherbiologically active compounds or entomopathogenic bacteria, virus orfungi to form a multi-component pesticide giving an even broaderspectrum of agricultural protection. Thus the present invention alsopertains to a composition comprising a compound of Formula 1 (in afungicidally effective amount) and at least one additional biologicallyactive compound or agent (in a biologically effective amount) and canfurther comprise at least one of a surfactant, a solid diluent or aliquid diluent. The other biologically active compounds or agents can beformulated in compositions comprising at least one of a surfactant,solid or liquid diluent. For mixtures of the present invention, one ormore other biologically active compounds or agents can be formulatedtogether with a compound of Formula 1, to form a premix, or one or moreother biologically active compounds or agents can be formulatedseparately from the compound of Formula 1, and the formulations combinedtogether before application (e.g., in a spray tank) or, alternatively,applied in succession.

Of note is a composition which in addition to the compound of Formula 1include at least one fungicidal compound selected from the groupconsisting of the classes (1) methyl benzimidazole carbamate (MBC)fungicides; (2) dicarboximide fungicides; (3) demethylation inhibitor(DMI) fungicides; (4) phenylamide fungicides; (5) amine/morpholinefungicides; (6) phospholipid biosynthesis inhibitor fungicides; (7)carboxamide fungicides; (8) hydroxy(2-amino-)pyrimidine fungicides; (9)anilinopyrimidine fungicides; (10)N-phenyl carbamate fungicides; (11)quinone outside inhibitor (QoI) fungicides; (12) phenylpyrrolefungicides; (13) quinoline fungicides; (14) lipid peroxidation inhibitorfungicides; (15) melanin biosynthesis inhibitors-reductase (MBI-R)fungicides; (16) melanin biosynthesis inhibitors-dehydratase (MBI-D)fungicides; (17) hydroxyanilide fungicides; (18) squalene-epoxidaseinhibitor fungicides; (19) polyoxin fungicides; (20) phenylureafungicides; (21) quinone inside inhibitor (QiI) fungicides; (22)benzamide fungicides; (23) enopyranuronic acid antibiotic fungicides;(24) hexopyranosyl antibiotic fungicides; (25) glucopyranosylantibiotic: protein synthesis fungicides; (26) glucopyranosylantibiotic: trehalase and inositol biosynthesis fungicides; (27)cyanoacetamideoxime fungicides; (28) carbamate fungicides; (29)oxidative phosphorylation uncoupling fungicides; (30) organo tinfungicides; (31) carboxylic acid fungicides; (32) heteroaromaticfungicides; (33) phosphonate fungicides; (34) phthalamic acidfungicides; (35) benzotriazine fungicides; (36) benzene-sulfonamidefungicides; (37) pyridazinone fungicides; (38) thiophene-carboxamidefungicides; (39) pyrimidinamide fungicides; (40) carboxylic acid amide(CAA) fungicides; (41) tetracycline antibiotic fungicides; (42)thiocarbamate fungicides; (43) benzamide fungicides; (44) host plantdefense induction fungicides; (45) multi-site contact activityfungicides; (46) fungicides other than classes (1) through (45); andsalts of compounds of classes (1) through (46).

Further descriptions of these classes of fungicidal compounds areprovided below.

(1) “Methyl benzimidazole carbamate (MBC) fungicides” (FungicideResistance Action Committee (FRAC) code 1) inhibit mitosis by binding toβ-tubulin during microtubule assembly. Inhibition of microtubuleassembly can disrupt cell division, transport within the cell and cellstructure. Methyl benzimidazole carbamate fungicides includebenzimidazoles and thiophanates. The benzimidazoles include benomyl,carbendazim, fuberidazole and thiabendazole. The thiophanates includethiophanate and thiophanate-methyl.

(2) “Dicarboximide fungicides” (Fungicide Resistance Action Committee(FRAC) code 2) are proposed to inhibit a lipid peroxidation in fungithrough interference with NADH cytochrome c reductase. Examples includechlozolinate, iprodione, procymidone and vinclozolin.

(3) “Demethylation inhibitor (DMI) fungicides” (Fungicide ResistanceAction Committee (FRAC) code 3) inhibit C14-demethylase, which plays arole in sterol production. Sterols, such as ergosterol, are needed formembrane structure and function, making them essential for thedevelopment of functional cell walls. Therefore, exposure to thesefungicides results in abnormal growth and eventually death of sensitivefungi. Demethylation fungicides include piperazines, pyridines,pyrimidines, imidazoles and triazoles. The piperazines includetriforine. The pyridines include buthiobate and pyrifenox. Thepyrimidines include fenarimol, nuarimol and triarimol. The imidazolesinclude clotrimazole, imazalil, oxpoconazole, prochloraz, pefurazoateand triflumizole. The triazoles include azaconazole, bitertanol,bromuconazole, cyproconazole, difenoconazole, diniconazole (includingdiniconazole-M), epoxiconazole, etaconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole,ipconazole, metconazole, myclobutanil, penconazole, propiconazole,prothioconazole, quinconazole, simeconazole, tebuconazole,tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole,1-[[(2S,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole,2-[[(2S,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thioneand1-[[(2S,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole.The imidazoles include clotrimazole, imazalil, oxpoconazole, prochloraz,pefurazoate and triflumizole. Biochemical investigations have shown thatall of the above mentioned fungicides are DMI fungicides as described byK. H. Kuck et al. in Modern Selective Fungicides—Properties,Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav FischerVerlag: New York, 1995, 205-258.

(4) “Phenylamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 4) are specific inhibitors of RNA polymerase in Oomycetefungi. Sensitive fungi exposed to these fungicides show a reducedcapacity to incorporate uridine into rRNA. Growth and development insensitive fungi is prevented by exposure to this class of fungicide.Phenylamide fungicides include acylalanines, oxazolidinones andbutyrolactones. The acylalanines include benalaxyl, benalaxyl-M,furalaxyl, metalaxyl and metalaxyl-M/mefenoxam. The oxazolidinonesinclude oxadixyl. The butyrolactones include ofurace.

(5) “Amine/morpholine fungicides” (Fungicide Resistance Action Committee(FRAC) code 5) inhibit two target sites within the sterol biosyntheticpathway, Δ⁸→Δ⁷ isomerase and Δ¹⁴ reductase. Sterols, such as ergosterol,are needed for membrane structure and function, making them essentialfor the development of functional cell walls. Therefore, exposure tothese fungicides results in abnormal growth and eventually death ofsensitive fungi. Amine/morpholine fungicides (also known as non-DMIsterol biosynthesis inhibitors) include morpholines, piperidines andspiroketal-amines. The morpholines include aldimorph, dodemorph,fenpropimorph, tridemorph and trimorphamide. The piperidines includefenpropidin and piperalin. The spiroketal-amines include spiroxamine.

(6) “Phospholipid biosynthesis inhibitor fungicides” (FungicideResistance Action Committee (FRAC) code 6) inhibit growth of fungi byaffecting phospholipid biosynthesis. Phospholipid biosynthesisfungicides include phophorothiolates and dithiolanes. Thephosphorothiolates include edifenphos, iprobenfos and pyrazophos. Thedithiolanes include isoprothiolane.

(7) “Carboxamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 7) inhibit Complex II (succinate dehydrogenase) fungalrespiration by disrupting a key enzyme in the Krebs Cycle (TCA cycle)named succinate dehydrogenase. Inhibiting respiration prevents thefungus from making ATP, and thus inhibits growth and reproduction.Carboxamide fungicides include phenyl benzamides, pyridinyl ethylbenzamides, furan carboxamides, oxathiin carboxamides, thiazolecarboxamides, pyrazole carboxamides and pyridine carboxamides. Thephenyl benzamides include benodanil, flutolanil and mepronil. Thepyridinyl ethyl benzamides include fluopyram. The furan carboxamidesinclude fenfuram. The oxathiin carboxamides include carboxin andoxycarboxin. The thiazole carboxamides include thifluzamide. Thepyrazole carboxamides include furametpyr, penthiopyrad, bixafen,isopyrazam, benzovindiflupyr,N-[2-(1S,2R)-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,penflufen,(N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide),N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamideandN-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methylethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide.The pyridine carboxamides include boscalid.

(8) “Hydroxy(2-amino-)pyrimidine fungicides” (Fungicide ResistanceAction Committee (FRAC) code 8) inhibit nucleic acid synthesis byinterfering with adenosine deaminase. Examples include bupirimate,dimethirimol and ethirimol.

(9) “Anilinopyrimidine fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 9) are proposed to inhibit biosynthesis of theamino acid methionine and to disrupt the secretion of hydrolytic enzymesthat lyse plant cells during infection. Examples include cyprodinil,mepanipyrim and pyrimethanil.

(10) “N-Phenyl carbamate fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 10) inhibit mitosis by binding to β-tubulin anddisrupting microtubule assembly. Inhibition of microtubule assembly candisrupt cell division, transport within the cell and cell structure.Examples include diethofencarb.

(11) “Quinone outside inhibitor (QoI) fungicides” (Fungicide ResistanceAction Committee (FRAC) code 11) inhibit Complex III mitochondrialrespiration in fungi by affecting ubiquinol oxidase. Oxidation ofubiquinol is blocked at the “quinone outside” (Q_(o)) site of thecytochrome bc₁ complex, which is located in the inner mitochondrialmembrane of fungi. Inhibiting mitochondrial respiration prevents normalfungal growth and development. Quinone outside inhibitor fungicides(also known as strobilurin fungicides) include methoxyacrylates,methoxycarbamates, oximinoacetates, oximinoacetamides,oxazolidinediones, dihydrodioxazines, imidazolinones andbenzylcarbamates. The methoxyacrylates include azoxystrobin,coumoxystrobin, enestroburin, flufenoxystrobin, picoxystrobin andpyraoxystrobin. The methoxycarbamates include pyraclostrobin,pyrametostrobin and triclopyricarb. The oximinoacetates includekresoxim-methyl and trifloxystrobin. The oximinoacetamides includedimoxystrobin, metominostrobin, orysastrobin,α-[methoxyimino]-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]-methyl]benzeneacetamideand2-[[[3-(2,6-dichlorophenyl)-1-methyl-2-propen-1-ylidene]-amino]oxy]methyl]-α-(methoxyimino)-N-methylbenzeneacetamide.The oxazolidinediones include famoxadone. The dihydrodioxazines includefluoxastrobin. The imidazolinones include fenamidone. Thebenzylcarbamates include pyribencarb. Class (11) also includes2-[(2,5-dimethylphenoxy)methyl]-ca-methoxy-N-benzeneacetamide.

(12) “Phenylpyrrole fungicides” (Fungicide Resistance Action Committee(FRAC) code 12) inhibit a MAP protein kinase associated with osmoticsignal transduction in fungi. Fenpiclonil and fludioxonil are examplesof this fungicide class.

(13) “Azanaphthalene fungicides” (Fungicide Resistance Action Committee(FRAC) code 13) are proposed to inhibit signal transduction by affectingG-proteins in early cell signaling. They have been shown to interferewith germination and/or appressorium formation in fungi that causepowder mildew diseases. Azanaphthalene fungicides includearyloxyquinolines and quinazolinone. The aryloxyquinolines includequinoxyfen and tebufloquin. The quinazolinones include proquinazid.

(14) “Lipid peroxidation inhibitor fungicides” (Fungicide ResistanceAction Committee (FRAC) code 14) are proposed to inhibit lipidperoxidation which affects membrane synthesis in fungi. Members of thisclass, such as etridiazole, may also affect other biological processessuch as respiration and melanin biosynthesis. Lipid peroxidationfungicides include aromatic carbons and 1,2,4-thiadiazoles. The aromaticcarbon fungicides include biphenyl, chloroneb, dicloran, quintozene,tecnazene and tolclofos-methyl. The 1,2,4-thiadiazole fungicides includeetridiazole.

(15) “Melanin biosynthesis inhibitors-reductase (MBI-R) fungicides”(Fungicide Resistance Action Committee (FRAC) code 16.1) inhibit thenaphthal reduction step in melanin biosynthesis. Melanin is required forhost plant infection by some fungi. Melanin biosynthesisinhibitors-reductase fungicides include isobenzofuranones,pyrroloquinolinones and triazolobenzothiazoles. The isobenzofuranonesinclude fthalide. The pyrroloquinolinones include pyroquilon. Thetriazolobenzothiazoles include tricyclazole.

(16) “Melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides”(Fungicide Resistance Action Committee (FRAC) code 16.2) inhibitscytalone dehydratase in melanin biosynthesis. Melanin in required forhost plant infection by some fungi. Melanin biosynthesisinhibitors-dehydratase fungicides include cyclopropanecarboxamides,carboxamides and propionamides. The cyclopropanecarboxamides includecarpropamid. The carboxamides include diclocymet. The propionamidesinclude fenoxanil.

(17) “Hydroxyanilide fungicides (Fungicide Resistance Action Committee(FRAC) code 17) inhibit C4-demethylase which plays a role in sterolproduction. Examples include fenhexamid.

(18) “Squalene-epoxidase inhibitor fungicides” (Fungicide ResistanceAction Committee (FRAC) code 18) inhibit squalene-epoxidase inergosterol biosynthesis pathway. Sterols such as ergosterol are neededfor membrane structure and function, making them essential for thedevelopment of functional cell walls. Therefore exposure to thesefungicides results in abnormal growth and eventually death of sensitivefungi. Squalene-epoxidase inhibitor fungicides include thiocarbamatesand allylaminess. The thiocarbamates include pyributicarb. Theallylamines include naftifine and terbinafine.

(19) “Polyoxin fungicides” (Fungicide Resistance Action Committee (FRAC)code 19) inhibit chitin synthase. Examples include polyoxin.

(20) “Phenylurea fungicides” (Fungicide Resistance Action Committee(FRAC) code 20) are proposed to affect cell division. Examples includepencycuron.

(21) “Quinone inside inhibitor (QiI) fungicides” (Fungicide ResistanceAction Committee (FRAC) code 21) inhibit Complex III mitochondrialrespiration in fungi by affecting ubiquinol reductase. Reduction ofubiquinol is blocked at the “quinone inside” (Q_(i)) site of thecytochrome bc₁ complex, which is located in the inner mitochondrialmembrane of fungi. Inhibiting mitochondrial respiration prevents normalfungal growth and development. Quinone inside inhibitor fungicidesinclude cyanoimidazoles and sulfamoyltriazoles. The cyanoimidazolesinclude cyazofamid. The sulfamoyltriazoles include amisulbrom.

(22) “Benzamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 22) inhibit mitosis by binding to β-tubulin and disruptingmicrotubule assembly. Inhibition of microtubule assembly can disruptcell division, transport within the cell and cell structure. Examplesinclude zoxamide.

(23) “Enopyranuronic acid antibiotic fungicides” (Fungicide ResistanceAction Committee (FRAC) code 23) inhibit growth of fungi by affectingprotein biosynthesis. Examples include blasticidin-S.

(24) “Hexopyranosyl antibiotic fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 24) inhibit growth of fungi by affecting proteinbiosynthesis. Examples include kasugamycin.

(25) “Glucopyranosyl antibiotic: protein synthesis fungicides”(Fungicide Resistance Action Committee (FRAC) code 25) inhibit growth offungi by affecting protein biosynthesis. Examples include streptomycin.

(26) “Glucopyranosyl antibiotic: trehalase and inositol biosynthesisfungicides” (Fungicide Resistance Action Committee (FRAC) code 26)inhibit trehalase in inositol biosynthesis pathway. Examples includevalidamycin.

(27) “Cyanoacetamideoxime fungicides (Fungicide Resistance ActionCommittee (FRAC) code 27) include cymoxanil.

(28) “Carbamate fungicides” (Fungicide Resistance Action Committee(FRAC) code 28) are considered multi-site inhibitors of fungal growth.They are proposed to interfere with the synthesis of fatty acids in cellmembranes, which then disrupts cell membrane permeability. Propamacarb,propamacarb-hydrochloride, iodocarb, and prothiocarb are examples ofthis fungicide class.

(29) “Oxidative phosphorylation uncoupling fungicides” (FungicideResistance Action Committee (FRAC) code 29) inhibit fungal respirationby uncoupling oxidative phosphorylation. Inhibiting respiration preventsnormal fungal growth and development. This class includes2,6-dinitroanilines such as fluazinam, pyrimidonehydrazones such asferimzone and dinitrophenyl crotonates such as dinocap, meptyldinocapand binapacryl.

(30) “Organo tin fungicides” (Fungicide Resistance Action Committee(FRAC) code 30) inhibit adenosine triphosphate (ATP) synthase inoxidative phosphorylation pathway. Examples include fentin acetate,fentin chloride and fentin hydroxide.

(31) “Carboxylic acid fungicides” (Fungicide Resistance Action Committee(FRAC) code 31) inhibit growth of fungi by affecting deoxyribonucleicacid (DNA) topoisomerase type II (gyrase). Examples include oxolinicacid.

(32) “Heteroaromatic fungicides” (Fungicide Resistance Action Committee(FRAC) code 32) are proposed to affect DNA/ribonucleic acid (RNA)synthesis. Heteroaromatic fungicides include isoxazoles andisothiazolones. The isoxazoles include hymexazole and the isothiazolonesinclude octhilinone.

(33) “Phosphonate fungicides” (Fungicide Resistance Action Committee(FRAC) code 33) include phosphorous acid and its various salts,including fosetyl-aluminum.

(34) “Phthalamic acid fungicides” (Fungicide Resistance Action Committee(FRAC) code 34) include teclofthalam.

(35) “Benzotriazine fungicides” (Fungicide Resistance Action Committee(FRAC) code 35) include triazoxide.

(36) “Benzene-sulfonamide fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 36) include flusulfamide.

(37) “Pyridazinone fungicides” (Fungicide Resistance Action Committee(FRAC) code 37) include diclomezine.

(38) “Thiophene-carboxamide fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 38) are proposed to affect ATP production.Examples include silthiofam.

(39) “Pyrimidinamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 39) inhibit growth of fungi by affecting phospholipidbiosynthesis and include diflumetorim.

(40) “Carboxylic acid amide (CAA) fungicides” (Fungicide ResistanceAction Committee (FRAC) code 40) are proposed to inhibit phospholipidbiosynthesis and cell wall deposition. Inhibition of these processesprevents growth and leads to death of the target fungus. Carboxylic acidamide fungicides include cinnamic acid amides, valinamide carbamates,carbamates and mandelic acid amides. The cinnamic acid amides includedimethomorph and flumorph. The valinamide carbamates includebenthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valifenalateand valiphenal. The carbamates include tolprocarb. The mandelic acidamides include mandipropamid,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)-amino]butanamideandN-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]-ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.

(41) “Tetracycline antibiotic fungicides” (Fungicide Resistance ActionCommittee (FRAC) code 41) inhibit growth of fungi by affecting complex 1nicotinamide adenine dinucleotide (NADH) oxidoreductase. Examplesinclude oxytetracycline.

(42) “Thiocarbamate fungicides” (Fungicide Resistance Action Committee(FRAC) code 42) include methasulfocarb.

(43) “Benzamide fungicides” (Fungicide Resistance Action Committee(FRAC) code 43) inhibit growth of fungi by delocalization ofspectrin-like proteins. Examples include acylpicolide fungicides such asfluopicolide.

(44) “Host plant defense induction fungicides” (Fungicide ResistanceAction Committee (FRAC) code P) induce host plant defense mechanisms.Host plant defense induction fungicides include benzothiadiazoles,benzisothiazoles and thiadiazolecarboxamides. The benzothiadiazolesinclude acibenzolar-S-methyl. The benzisothiazoles include probenazole.The thiadiazolecarboxamides include tiadinil and isotianil.

(45) “Multi-site contact fungicides” inhibit fungal growth throughmultiple sites of action and have contact/preventive activity. Thisclass of fungicides includes: (45.1) “copper fungicides” (FungicideResistance Action Committee (FRAC) code M1)”, (45.2) “sulfur fungicides”(Fungicide Resistance Action Committee (FRAC) code M2), (45.3)“dithiocarbamate fungicides” (Fungicide Resistance Action Committee(FRAC) code M3), (45.4) “phthalimide fungicides” (Fungicide ResistanceAction Committee (FRAC) code M4), (45.5) “chloronitrile fungicides”(Fungicide Resistance Action Committee (FRAC) code M5), (45.6)“sulfamide fungicides” (Fungicide Resistance Action Committee (FRAC)code M6), (45.7) “guanidine fungicides” (Fungicide Resistance ActionCommittee (FRAC) code M7), (45.8) “triazine fungicides” (FungicideResistance Action Committee (FRAC) code M8) and (45.9) “quinonefungicides” (Fungicide Resistance Action Committee (FRAC) code M9).“Copper fungicides” are inorganic compounds containing copper, typicallyin the copper(II) oxidation state; examples include copper oxychloride,copper sulfate and copper hydroxide, including compositions such asBordeaux mixture (tribasic copper sulfate). “Sulfur fungicides” areinorganic chemicals containing rings or chains of sulfur atoms; examplesinclude elemental sulfur. “Dithiocarbamate fungicides” contain adithiocarbamate molecular moiety; examples include mancozeb, metiram,propineb, ferbam, maneb, thiram, zineb and ziram. “Phthalimidefungicides” contain a phthalimide molecular moiety; examples includefolpet, captan and captafol. “Chloronitrile fungicides” contain anaromatic ring substituted with chloro and cyano; examples includechlorothalonil. “Sulfamide fungicides” include dichlofluanid andtolyfluanid. “Guanidine fungicides” include dodine, guazatine,iminoctadine albesilate and iminoctadine triacetate. “Triazinefungicides” include anilazine. “Quinone fungicides” include dithianon.

(46) “Fungicides other than fungicides of classes (1) through (45)”include certain fungicides whose mode of action may be unknown. Theseinclude: (46.1) “thiazole carboxamide fungicides” (Fungicide ResistanceAction Committee (FRAC) code U5), (46.2) “phenylacetamide fungicides”(Fungicide Resistance Action Committee (FRAC) code U6), (46.3)“arylphenylketone fungicides” (Fungicide Resistance Action Committee(FRAC) code U8) and (46.4) “triazolopyrimidine fungicides”. The thiazolecarboxamides include ethaboxam. The phenylacetamides includecyflufenamid andN-[[(cyclopropylmethoxy)-amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]benzeneacetamide.The arylphenylketones include benzophenones such as metrafenone andbenzoylpyridines such as pyriofenone. The triazolopyrimidines includeametoctradin. Class (46) (i.e. “Fungicides other than classes (1)through (45)”) also includes bethoxazin, fluxapyroxad, neo-asozin(ferric methanearsonate), pyrrolnitrin, quinomethionate, tebufloquin,isofetamid,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide,2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile,3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine,4-fluorophenylN-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate,5-chloro-6-(2,4,6-trifluorophenyl)-7-(4-methylpiperidin-1-yl)[1,2,4]triazolo[1,5-a]pyrimidine,N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide,N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide,N-[4-[4-chloro-3-(trifluoromethyl)-phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,1-[(2-propenylthio)-carbonyl]-2-(1-methylethyl)-4-(2-methylphenyl)-5-amino-1H-pyrazol-3-one,N-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,1,1-dimethylethylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]-amino]oxy]methyl]-2-pyridinyl]carbamate,3-butyn-1-ylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate,2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone,5-fluoro-2-[(4-methylphenyl)-methoxy]-4-pyrimidinamine,5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine,α-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]pyrid-3-ylmethanol,(aS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]pyrid-3-ylmethanoland(aR)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]pyrid-3-ylmethanol.

Therefore of note is a mixture (i.e. composition) comprising a compoundof Formula 1 and at least one fungicidal compound selected from thegroup consisting of the aforedescribed classes (1) through (46). Also ofnote is a composition comprising said mixture (in fungicidally effectiveamount) and further comprising at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents. Of particular note is a mixture (i.e. composition)comprising a compound of Formula 1 and at least one fungicidal compoundselected from the group of specific compounds listed above in connectionwith classes (1) through (46). Also of particular note is a compositioncomprising said mixture (in fungicidally effective amount) and furthercomprising at least one additional surfactant selected from the groupconsisting of surfactants, solid diluents and liquid diluents.

Examples of other biologically active compounds or agents with whichcompounds of this invention can be formulated are: insecticides such asabamectin, acephate, acetamiprid, acrinathrin, amidoflumet (S-1955),avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate,buprofezin, carbofuran, cartap, chlorantraniliprole, chlorfenapyr,chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,clothianidin, cyantraniliprole(3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide),cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin,diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin,dimethoate, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin,fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate,tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonophos,halofenozide, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb,isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone,metaldehyde, methamidophos, methidathion, methomyl, methoprene,methoxychlor, methoxyfenozide, metofluthrin, milbemycin oxime,monocrotophos, nicotine, nitenpyram, nithiazine, novaluron, noviflumuron(XDE-007), oxamyl, parathion, parathion-methyl, permethrin, phorate,phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin,pymetrozine, pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon,pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad,spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulfoxaflor,sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos,tetrachlorvinphos, tetramethylfluthrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon and triflumuron; and biological agents includingentomopathogenic bacteria, such as Bacillus thuringiensis subsp.aizawai, Bacillus thuringiensis subsp. kurstaki, and the encapsulateddelta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII);entomopathogenic fungi, such as green muscardine fungus; andentomopathogenic virus including baculovirus, nucleopolyhedro virus(NPV) such as HzNPV, AfNPV; and granulosis virus (GV) such as CpGV.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). The effect ofthe exogenously applied fungicidal compounds of this invention may besynergistic with the expressed toxin proteins.

General references for agricultural protectants (i.e. insecticides,fungicides, nematocides, acaricides, herbicides and biological agents)include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed.,British Crop Protection Council, Farnham, Surrey, U. K., 2003 and TheBioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British CropProtection Council, Farnham, Surrey, U. K., 2001.

For embodiments where one or more of these various mixing partners areused, the weight ratio of these various mixing partners (in total) tothe compound of Formula 1 is typically between about 1:3000 and about3000:1. Of note are weight ratios between about 1:300 and about 300:1(for example ratios between about 1:30 and about 30:1). One skilled inthe art can easily determine through simple experimentation thebiologically effective amounts of active ingredients necessary for thedesired spectrum of biological activity. It will be evident thatincluding these additional components may expand the spectrum ofdiseases controlled beyond the spectrum controlled by the compound ofFormula 1 alone.

In certain instances, combinations of a compound of this invention withother biologically active (particularly fungicidal) compounds or agents(i.e. active ingredients) can result in a greater-than-additive (i.e.synergistic) effect. Reducing the quantity of active ingredientsreleased in the environment while ensuring effective pest control isalways desirable. When synergism of fungicidal active ingredients occursat application rates giving agronomically satisfactory levels of fungalcontrol, such combinations can be advantageous for reducing cropproduction cost and decreasing environmental load.

Of note is a combination of a compound of Formula 1 with at least oneother fungicidal active ingredient. Of particular note is such acombination where the other fungicidal active ingredient has differentsite of action from the compound of Formula 1. In certain instances, acombination with at least one other fungicidal active ingredient havinga similar spectrum of control but a different site of action will beparticularly advantageous for resistance management. Thus, a compositionof the present invention can further comprise a biologically effectiveamount of at least one additional fungicidal active ingredient having asimilar spectrum of control but a different site of action.

Of particular note are compositions which in addition to compound ofFormula 1 include at least one compound selected from the groupconsisting of (1) alkylenebis(dithiocarbamate) fungicides; (2)cymoxanil; (3) phenylamide fungicides; (4) proquinazid(6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone); (5) chlorothalonil;(6) carboxamides acting at complex II of the fungal mitochondrialrespiratory electron transfer site; (7) quinoxyfen; (8) metrafenone; (9)cyflufenamid; (10) cyprodinil; (11) copper compounds; (12) phthalimidefungicides; (13) fosetyl-aluminum; (14) benzimidazole fungicides; (15)cyazofamid; (16) fluazinam; (17) iprovalicarb; (18) propamocarb; (19)validomycin; (20) dichlorophenyl dicarboximide fungicides; (21)zoxamide; (22) fluopicolide; (23) mandipropamid; (24) carboxylic acidamides acting on phospholipid biosynthesis and cell wall deposition;(25) dimethomorph; (26) non-DMI sterol biosynthesis inhibitors; (27)inhibitors of demethylase in sterol biosynthesis; (28) bc₁ complexfungicides; and salts of compounds of (1) through (28).

Further descriptions of classes of fungicidal compounds are providedbelow.

Sterol biosynthesis inhibitors (group (27)) control fungi by inhibitingenzymes in the sterol biosynthesis pathway. Demethylase-inhibitingfungicides have a common site of action within the fungal sterolbiosynthesis pathway, involving inhibition of demethylation at position14 of lanosterol or 24-methylene dihydrolanosterol, which are precursorsto sterols in fungi. Compounds acting at this site are often referred toas demethylase inhibitors, DMI fungicides, or DMIs. The demethylaseenzyme is sometimes referred to by other names in the biochemicalliterature, including cytochrome P-450 (14DM). The demethylase enzyme isdescribed in, for example, J. Biol. Chem. 1992, 267, 13175-79 andreferences cited therein. DMI fungicides are divided between severalchemical classes: azoles (including triazoles and imidazoles),pyrimidines, piperazines and pyridines. The triazoles includeazaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole(including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole,ipconazole, metconazole, myclobutanil, penconazole, propiconazole,prothioconazole, quinconazole, simeconazole, tebuconazole,tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole.The imidazoles include clotrimazole, econazole, imazalil, isoconazole,miconazole, oxpoconazole, prochloraz and triflumizole. The pyrimidinesinclude fenarimol, nuarimol and triarimol. The piperazines includetriforine. The pyridines include buthiobate and pyrifenox. Biochemicalinvestigations have shown that all of the above mentioned fungicides areDMI fungicides as described by K. H. Kuck et al. in Modern SelectiveFungicides-Properties, Applications and Mechanisms of Action, H. Lyr(Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

bc₁ Complex Fungicides (group 28) have a fungicidal mode of action whichinhibits the bc₁ complex in the mitochondrial respiration chain. The bc₁complex is sometimes referred to by other names in the biochemicalliterature, including complex III of the electron transfer chain, andubihydroquinone:cytochrome c oxidoreductase. This complex is uniquelyidentified by Enzyme Commission number EC1.10.2.2. The bc₁ complex isdescribed in, for example, J. Biol. Chem. 1989, 264, 14543-48; MethodsEnzymol. 1986, 126, 253-71; and references cited therein. Strobilurinfungicides such as azoxystrobin, dimoxystrobin, enestroburin (SYP-Z071),fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin,picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin andtrifloxystrobin are known to have this mode of action (H. Sauter et al.,Angew. Chem. Int. Ed. 1999, 38, 1328-1349). Other fungicidal compoundsthat inhibit the bc₁ complex in the mitochondrial respiration chaininclude famoxadone and fenamidone.

Alkylenebis(dithiocarbamate)s (group (1)) include compounds such asmancozeb, maneb, propineb and zineb. Phenylamides (group (3)) includecompounds such as metalaxyl, benalaxyl, furalaxyl and oxadixyl.Carboxamides (group (6)) include compounds such as boscalid, carboxin,fenfuram, flutolanil, furametpyr, mepronil, oxycarboxin, thifluzamide,penthiopyrad andN-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide(PCT Patent Publication WO 2003/010149), and are known to inhibitmitochondrial function by disrupting complex II (succinatedehydrogenase) in the respiratory electron transport chain. Coppercompounds (group (11)) include compounds such as copper oxychloride,copper sulfate and copper hydroxide, including compositions such asBordeaux mixture (tribasic copper sulfate). Phthalimides (group (12))include compounds such as folpet and captan. Benzimidazole fungicides(group (14)) include benomyl and carbendazim. Dichlorophenyldicarboximide fungicides (group (20)) include chlozolinate,dichlozoline, iprodione, isovaledione, myclozolin, procymidone andvinclozolin.

Non-DMI sterol biosynthesis inhibitors (group (26)) include morpholineand piperidine fungicides. The morpholines and piperidines are sterolbiosynthesis inhibitors that have been shown to inhibit steps in thesterol biosynthesis pathway at a point later than the inhibitionsachieved by the DMI sterol biosynthesis (group (27)). The morpholinesinclude aldimorph, dodemorph, fenpropimorph, tridemorph andtrimorphamide. The piperidines include fenpropidin.

The control efficacy of compounds of this invention on specificpathogens is demonstrated in TABLE A below. The pathogen controlprotection afforded by the compounds is not limited, however, to thespecies described in Tests A-E below. Descriptions of the compounds areprovided in Index Table A. The following abbreviations are used in theindex table: Ph is phenyl, “Cmpd. No.” means compound number, and “Ex.”stands for “Example” and is followed by a number indicating in whichexample the compound is prepared.

INDEX TABLE A

Cmpd. No. Q² R^(3b) m.p. (° C.)  1 2-C1-4-F—Ph

141-143  2 2-C1-4-F—Ph

114-117  3 (Ex. 1) 2-C1-4-F—Ph

192-194  4 2-C1-4-F—Ph

216-219  5 2-C1-4-F—Ph

165-168  6 2-C1-4-F—Ph

146-149  7 2-C1-4-F—Ph

170-172  8 2-C1-4-F—Ph

161-164  9 (Ex. 3) 2-C1-4-F—Ph

159-162 10 (Ex. 2) 2-C1-4-F—Ph

167-170 11 2-C1-4-F—Ph

224-227 12 2-C1-4-F—Ph

175-178 13 2-C1-4-F—Ph

177-180 14 2-C1-4-F—Ph

139-142 15 2-C1-4-F—Ph

172-175 16 2-C1-4-F—Ph

146-149 17 2-C1-4-F—Ph

148-150 18 2-C1-4-F—Ph

174-177 19 2-C1-4-F—Ph

162-165

Biological Examples of the Invention

General protocol for preparing test suspensions for Tests A-E: the testcompounds were first dissolved in acetone in an amount equal to 3% ofthe final volume and then suspended at the desired concentration (inppm) in acetone and purified water (50/50 mix by volume) containing 250ppm of the surfactant Trem® 014 (polyhydric alcohol esters). Theresulting test suspensions were then used in Tests A-E. Spraying a 200ppm test suspension to the point of run-off on the test plants was theequivalent of a rate of 800 g/ha.

Test A

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Puccinia recondita f. sp. tritici (the causal agent ofwheat leaf rust) and incubated in a saturated atmosphere at 20° C. for24 h, and then moved to a growth chamber at 20° C. for 6 days, afterwhich time visual disease ratings were made.

Test B

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Septoria tritici (the causal agent of wheat leaf blotch)and incubated in a saturated atmosphere at 24° C. for 48 h, and thenmoved to a growth chamber at 20° C. for 19 days, after which time visualdisease ratings were made.

Test C

The test suspension was sprayed to the point of run-off on tomatoseedlings. The following day the seedlings were inoculated with a sporesuspension of Botrytis cinerea (the causal agent of tomato Botrytis) andincubated in a saturated atmosphere at 20° C. for 48 h, and then movedto a growth chamber at 24° C. for 3 days, after which time visualdisease ratings were made.

Test D

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporedust of Blumeria graminis f. sp. tritici, also known as Erysiphegraminis f. sp. tritici (the causal agent of wheat powdery mildew) andincubated in a growth chamber at 20° C. for 8 days, after which timevisual disease ratings were made.

Test E

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Septoria nodorum (the causal agent of Septoria glumeblotch) and incubated in a saturated atmosphere at 24° C. for 48 h, andthen moved to a growth chamber at 20° C. for 9 days, after which timevisual disease ratings were made.

Results for Tests A-E are given in Table A. In the Table, a rating of100 indicates 100% disease control and a rating of 0 indicates nodisease control (relative to the controls). All results are forcompounds tested at 200 ppm except where followed by an asterisk “*”which indicates the compound was tested at 250 ppm. A dash (-) indicatesno test results.

TABLE A Cmpd. No Test A Test B Test C Test D Test E 1 68 —  0 98 0 2 95— 98 98 100  3 68 — 59 81 98  4  0 —  0  0 0 5 100  99 98 99 — 6 99 9999 95 — 7 99 — 97 93 — 8 90 95 30 27 0 9  9 87  0  21* 0 10 99 96 12 94100  11 86 98 15 69 0 12 89 95 97 73 0 13  0 98  0 98 — 14 100  99 39 95— 15  98* 100*  98*  95* — 16 100* 100*  97*  99* — 17 100*  99*  69*100* — 18 100*  99*  31*  99* — 19 100*  99* 100*  95* —

What is claimed is:
 1. A compound selected from Formula 1, N-oxides andsalts thereof,

wherein Q¹ is a phenyl ring or a naphthalenyl ring system, each ring orring system optionally substituted with up to 5 substituentsindependently selected from R^(3a) and R^(3b); or a 5- to 6-memberedfully unsaturated heterocyclic ring or an 8- to 10-memberedheteroaromatic bicyclic ring system, each ring or ring system containingring members selected from carbon atoms and 1 to 4 heteroatomsindependently selected from up to 2 O, up to 2 S and up to 4 N atoms,wherein up to 3 carbon ring members are independently selected fromC(═O) and C(═S), and the sulfur atom ring members are independentlyselected from S(═O)_(u)(═NR²⁷)_(v), each ring or ring system optionallysubstituted with up to 5 substituents independently selected from R^(3a)and R^(3b) on carbon atom ring members and selected from cyano, C₁-C₄alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, C₂-C₄alkoxyalkyl, C₁-C₄ alkoxy, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl,C₂-C₄ alkylaminoalkyl and C₃-C₄ dialkylaminoalkyl on nitrogen atom ringmembers; Q² is a phenyl ring or a naphthalenyl ring system, each ring orring system optionally substituted with up to 5 substituentsindependently selected from R^(3a) and R^(3b); or a 5- to 6-memberedfully unsaturated heterocyclic ring or an 8- to 10-memberedheteroaromatic bicyclic ring system, each ring or ring system containingring members selected from carbon atoms and 1 to 4 heteroatomsindependently selected from up to 2 O, up to 2 S and up to 4 N atoms,wherein up to 3 carbon ring members are independently selected fromC(═O) and C(═S), and the sulfur atom ring members are independentlyselected from S(═O)_(u)(═NR²⁷)_(v), each ring or ring system optionallysubstituted with up to 5 substituents independently selected from R^(3a)and R^(3b) on carbon atom ring members and selected from cyano, C₁-C₄alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, C₂-C₄alkoxyalkyl, C₁-C₄ alkoxy, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl,C₂-C₄ alkylaminoalkyl and C₃-C₄ dialkylaminoalkyl on nitrogen atom ringmembers; X is O, S(═O)_(m), NR⁴ or CR^(5a)OR^(5b); R¹ is H, cyano,halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl,C₃-C₆ cycloalkyl, C₂-C₆ alkoxyalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy,—C(═O)OR⁶ or —C(═O)NR⁷R⁸; R^(1a) is H; or R^(1a) and R¹ are takentogether with the carbon atom to which they are attached to form acyclopropyl ring optionally substituted with up to 2 substituentsindependently selected from halogen and methyl; R² is H, cyano, halogen,C₁-C₃ alkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, C₁-C₃ haloalkyl, C₂-C₃haloalkenyl, C₂-C₃ cyanoalkyl, C₁-C₃ hydroxyalkyl, C₁-C₃ alkoxy or C₁-C₃alkylthio; or cyclopropyl optionally substituted with up to 2substituents independently selected from halogen and methyl; each R^(3a)is independently amino, cyano, halogen, hydroxy, nitro, C₁-C₃ alkyl,C₁-C₃ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₄-C₆ cycloalkylalkyl, C₄-C₆ alkylcycloalkyl, C₁-C₃alkylthio, C₁-C₃ haloalkylthio, C₁-C₃ alkylsulfinyl, C₁-C₃haloalkylsulfinyl, C₁-C₃ alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₁-C₃alkoxy, C₁-C₃ haloalkoxy, C₃-C₆ cycloalkoxy, C₁-C₃ alkylsulfonyloxy,C₁-C₃ haloalkylsulfonyloxy, C₂-C₄ alkylcarbonyloxy, C₂-C₄ alkylcarbonyl,C₁-C₃ alkylamino, C₂-C₄ dialkylamino, C₂-C₄ alkylcarbonylamino, —CH(═O),—NHCH(═O), —SF₅, —SC≡N or —U—V-T; each R^(3b) is independently C₄-C₈alkyl, C₄-C₈ haloalkyl, C₅-C₈ alkenyl, C₂-C₈ haloalkenyl, C₅-C₈ alkynyl,C₂-C₈ haloalkynyl, C₁-C₈ nitroalkyl, C₂-C₈ nitroalkenyl, C₇-C₈cycloalkyl, C₇-C₈ halocycloalkyl, C₇-C₈ cycloalkylalkyl, C₇-C₈alkylcycloalkyl, C₅-C₁₂ cycloalkylalkenyl, C₅-C₁₂ cycloalkylalkynyl,C₆-C₁₂ cycloalkylcycloalkyl, C₄-C₈ alkylthio, C₄-C₈ haloalkythio, C₄-C₈alkylsulfinyl, C₄-C₈ haloalkylsulfinyl, C₄-C₈ alkylsulfonyl, C₄-C₈haloalkylsulfonyl, C₄-C₈ alkoxy, C₄-C₈ haloalkoxy, C₂-C₈ alkenyloxy,C₂-C₈ haloalkenyloxy, C₃-C₈ alkynyloxy, C₃-C₈ haloalkynyloxy, C₇-C₁₂cycloalkoxy, C₃-C₁₂ halocycloalkoxy, C₄-C₁₂ cycloalkylalkoxy, C₅-C₁₂cycloalkylalkenyloxy, C₅-C₁₂ cycloalkylalkynyloxy, C₄-C₈alkylsulfonyloxy, C₄-C₈ haloalkylsulfonyloxy, C₅-C₈ alkylcarbonyloxy,C₅-C₈ alkylcarbonyl, C₄-C₈ alkylamino, C₅-C₈ alkylcarbonylamino, C₃-C₁₂trialkylsilyl, C₄-C₁₂ trialkylsilylalkyl, C₄-C₁₂ trialkylsilylalkoxy,—C(═S)NR^(9a)R^(9b), —CR^(10a)═NOR^(10b), —CR^(10c)═NNR^(9a)R^(9b),—NR^(9a)N═CR^(11a)R^(11b), —ON═CR^(11a)R^(11b) or-A(CR^(12a)R^(12b))_(n)W; each A is independently O or a direct bond;each W is independently a 3- to 7-membered heterocyclic ring containingring members selected from carbon atoms and 1 to 4 heteroatomsindependently selected from up to 2 O, up to 2 S and up to 4 N atoms,wherein up to 3 carbon atom ring members are independently selected fromC(═O) and C(═S), the ring optionally substituted with up to 3substituents independently selected from R¹³ on carbon atom ring membersand R¹⁴ on nitrogen atom ring members; R⁴ is H, amino, C₂-C₆ alkenyl,C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, —CH(═O), —S(═O)₂OM, —S(═O)_(m)R¹⁵,—(C═Z)R¹⁶ or OR¹⁷; or C₁-C₆ alkyl or C₁-C₆ haloalkyl, each optionallysubstituted with up to 2 substituents independently selected from R¹⁸;R^(5a) is H or C₁-C₆ alkyl; R^(5b) is H, —CH(═O), C₁-C₆ alkyl, C₁-C₆haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₂-C₆ cyanoalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₄-C₈cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈(cycloalkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl) or C₄-C₈cycloalkoxy(thiocarbonyl); R⁶ is H, C₁-C₆ alkyl or C₁-C₆ haloalkyl; R⁷and R⁸ are each independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆cycloalkyl, C₄-C₈ cycloalkylalkyl or C₄-C₈ alkylcycloalkyl; or R⁷ and R⁸are taken together with the nitrogen atom to which they are attached toform a 4- to 7-membered nonaromatic heterocyclic ring containing ringmembers, in addition to the connecting nitrogen atom, selected fromcarbon atoms and up to 1 ring member selected from O, S(═O)_(m) andNR¹⁹; each R^(9a) and R^(9b) is independently H, C₁-C₄ alkyl or C₁-C₄haloalkyl; each R^(10a) is independently H, C₁-C₃ alkyl or C₁-C₃haloalkyl; each R^(10b) and R^(10c) is independently H, C₁-C₃ alkyl,C₁-C₃ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ haloalkenyl, C₂-C₄ alkynyl, C₃-C₄cycloalkyl, C₃-C₄ halocycloalkyl or C₄-C₈ cycloalkylalkyl; each R^(11a)and R^(11b) is independently H, C₁-C₃ alkyl or C₁-C₃ haloalkyl; eachR^(12a) is independently H, cyano, halogen or C₁-C₄ alkyl; each R^(12b)is independently H or C₁-C₄ alkyl; each R¹³ is independently cyano,halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy orC₂-C₄ alkoxyalkyl; each R¹⁴ is independently cyano, C₁-C₂ alkyl or C₁-C₂alkoxy; R¹⁵ is C₁-C₆ alkyl or C₁-C₆ haloalkyl; R¹⁶ is C₁-C₆ alkyl, C₂-C₆alkylthioalkyl, C₂-C₆ alkoxyalkyl, C₂-C₆ alkylaminoalkyl, C₃-C₆dialkylaminoalkyl, C₁-C₆ alkoxy or C₁-C₆ alkylthio; R¹⁷ is H, —CH(═O),C₃-C₆ cycloalkyl, —S(═O)₂OM or —(C═Z)R²⁰; or C₁-C₆ alkyl or C₁-C₆haloalkyl, each optionally substituted with up to 2 substituentsindependently selected from R²¹; each R¹⁸ and R²¹ is independentlycyano, C₃-C₆ cycloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₁-C₆alkylthio, C₁-C₆ alkylsulfinyl or C₁-C₆ alkylsulfonyl; R¹⁹ is H, C₁-C₃alkyl or C₂-C₃ haloalkyl; R²⁰ is C₁-C₆ alkyl, C₂-C₆ alkoxyalkyl, C₂-C₆alkylthioalkyl, C₂-C₆ alkylaminoalkyl, C₃-C₆ dialkylaminoalkyl, C₁-C₆alkoxy or C₁-C₆ alkylthio; each U is independently O, S(═O)_(m), NR²² ora direct bond; each V is independently C₁-C₆ alkylene, C₂-C₆ alkenylene,C₃-C₆ alkynylene, C₃-C₆ cycloalkylene or C₃-C₆ cycloalkenylene, whereinup to 3 carbon atoms are C(═O), each optionally substituted with up to 5substituents independently selected from halogen, cyano, nitro, hydroxy,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy and C₁-C₆ haloalkoxy; each Tis independently cyano, NR^(23a)R^(23b), OR²⁴ or S(═O)_(m)R²⁵; each R²²is independently H, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkylcarbonyl,C₂-C₆ alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₂-C₆alkoxy(thiocarbonyl), C₄-C₈ cycloalkylcarbonyl, C₄-C₈cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl or C₄-C₈cycloalkoxy(thiocarbonyl); each R^(23a) and R^(23b) is independently H,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₂-C₆ alkoxy(thiocarbonyl),C₄-C₈ cycloalkylcarbonyl, C₄-C₈ cycloalkoxycarbonyl, C₄-C₈(cycloalkylthio)carbonyl or C₄-C₈ cycloalkoxy(thiocarbonyl); or a pairof R^(23a) and R^(23b) attached to the same nitrogen atom are takentogether with the nitrogen atom to form a 3- to 6-membered heterocyclicring, the ring optionally substituted with up to 5 substituentsindependently selected from R²⁶; each R²⁴ and R²⁵ is independently H,C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₂-C₆ alkenyl, C₃-C₆ alkynyl, C₃-C₆cycloalkyl, C₃-C₆ halocycloalkyl, C₂-C₆ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ (alkylthio)carbonyl, C₄-C₈ cycloalkylcarbonyl,C₄-C₈ cycloalkoxycarbonyl, C₄-C₈ (cycloalkylthio)carbonyl, C₂-C₆alkoxy(thiocarbonyl) or C₄-C₈ cycloalkoxy(thiocarbonyl); each R²⁶ isindependently halogen, C₁-C₆ alkyl, C₁-C₆ haloalkyl or C₁-C₆ alkoxy;each R²⁷ is independently H, cyano, C₁-C₃ alkyl or C₁-C₃ haloalkyl; Z isO or S; M is K, Na or Li; each m is independently 0, 1 or 2; each n isindependently 0, 1, 2 or 3; and each u and v are independently 0, 1 or 2in each instance of S(═O)_(u)(═NR²⁷)_(v); provided that: (a) the sum ofu and v is 0, 1 or 2; (b) when Q¹ and Q² are each an optionallysubstituted phenyl ring, an optionally substituted naphthalenyl ringsystem, an optionally substituted 5- to 6-membered fully unsaturatedheterocyclic ring or an optionally substituted 8- to 10-memberedheteroaromatic bicyclic ring system, then at least one of Q¹ or Q² issubstituted with at least one R^(3b); and (c) when n is 1, 2, or 3, thenW is linked through a carbon atom to the remainder of Formula
 1. 2. Acompound of claim 1 wherein: Q¹ is a phenyl ring substituted at the 2-,4- and 6-positions with substituents independently selected from R^(3a)and R^(3b); or a phenyl ring substituted at the 2- and 4-positions withsubstituents independently selected from R^(3a) and R^(3b); or a phenylring substituted at the 2- and 6-positions with substituentsindependently selected from R^(3a) and R^(3b). Q² is a phenyl ringsubstituted at the 2-, 4- and 6-positions with substituentsindependently selected from R^(3a) and R^(3b); or a phenyl ringsubstituted at the 2- and 4-positions with substituents independentlyselected from R^(3a) and R^(3b); or a phenyl ring substituted at the 2-and 6-positions with substituents independently selected from R^(3a) andR^(3b). X is NR⁴ or CHOR^(5b); R¹ is H or methyl; R^(1a) is H; R² is Br,Cl or methyl; each R^(3a) is independently cyano, halogen or methoxy;each R^(3b) is independently C₅-C₈ cycloalkylalkynyl, C₄-C₆ alkoxy,C₄-C₆ haloalkoxy, C₂-C₆ alkenyloxy, C₂-C₆ haloalkenyloxy, C₃-C₆alkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₉ trialkylsilylalkoxy,—C(═S)NR^(9a)R^(9b), —CR^(10a)═NOR^(10b), —ON═CR^(11a)R^(11b) or-A(CR^(12a)R^(12b))_(n)W; each W is independently a 3- to 5-memberedheterocyclic ring containing ring members selected from carbon atoms and1 to 2 heteroatoms independently selected from up to 2 O and up to 2 Natoms, the ring optionally substituted with up to 2 substituentsindependently selected from R¹³ on carbon atom ring members; R⁴ is H;R^(5b) is H; each R^(9a) and R^(9b) is independently H or methyl; eachR^(10a) is independently H, methyl or halomethyl; each R^(10b) isindependently H, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₃-C₄ cycloalkyl or C₃-C₄halocycloalkyl; each R^(11a) and R^(11b) is independently H, methyl orhalomethyl; each R^(12a) is independently H, cyano, halogen or methyl;each R^(12b) is independently H or methyl; and each R¹³ is independentlyhalogen, methyl, halomethyl or methoxy.
 3. A compound of claim 2 whereinQ¹ is a phenyl ring substituted with 2 substituents independentlyselected from R^(3a) and 1 substituent selected from R^(3b); Q² is aphenyl ring substituted with 1 to 3 substituents independently selectedfrom R^(3a); X is CHOR^(5b); R¹ is H; R² is methyl; each R^(3a) isindependently Br, Cl or F; R^(3b) is C₅-C₈ cycloalkylalkynyl, C₄-C₆alkoxy, C₄-C₆ haloalkoxy, C₂-C₆ alkenyloxy, C₂-C₆ haloalkenyloxy, C₃-C₆alkynyloxy, C₄-C₈ cycloalkylalkoxy, C₄-C₉ trialkylsilylalkoxy,—CR^(10a)═NOR⁹, —ON═CR^(11a)R^(11b) or -A(CR^(12a)R^(12b))_(n)W; W is a3- to 5-membered heterocyclic ring containing ring members selected fromcarbon atoms and 1 to 2 heteroatoms independently selected from up to 2O and up to 2 N atoms; R^(12a) is H; R^(12b) is H; and n is 0, 1 or 2.4. A compound of claim 3 wherein Q¹ is a phenyl ring substituted with 2substituents independently selected from R^(3a) which are attached atthe 2- and 6-positions and 1 substituent selected from R^(3b) which isattached at the 4-position; Q² is a phenyl ring substituted with 2substituents independently selected from R^(3a) which are attached atthe 2- and 6-positions; or a phenyl ring substituted with 2 substituentsindependently selected from R^(3a) which R^(3b) is C₅-C₈cycloalkylalkynyl, C₄-C₆ alkoxy, C₄-C₆ haloalkoxy, C₂-C₆ alkenyloxy,C₂-C₆ haloalkenyloxy, C₃-C₆ alkynyloxy, C₄-C₈ cycloalkylalkoxy,—CR^(10a)═NOR⁹ or -A(CR^(12a)R^(12b))_(n)W.
 5. The compound of claim 1which is selected from the group:α-(2-chloro-4-fluorophenyl)-5-[2,6-difluoro-4-(1H-pyrazol-1-yl)phenyl]-1,3-dimethyl-1H-pyrazole-4-methanol;andα-(2-chloro-4-fluorophenyl)-5-[4-(2-cyclopropylethynyl)-2,6-difluorophenyl]-1,3-dimethyl-1H-pyrazole-4-methanol.6. A fungicidal composition comprising (a) a compound of claim 1; and(b) at least one other fungicide.
 7. A fungicidal composition comprising(a) a compound of claim 1; and (b) at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents.
 8. A method for controlling plant diseases caused byfungal plant pathogens comprising applying to the plant or portionthereof, or to the plant seed, a fungicidally effective amount of acompound of claim 1.